CN102365315A

CN102365315A - Hard coating composite, and resin substrate having a hard coat layer

Info

Publication number: CN102365315A
Application number: CN2010800141194A
Authority: CN
Inventors: 山本今日子; 澁谷崇; 宫岛达也
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2009-03-27
Filing date: 2010-03-25
Publication date: 2012-02-29
Anticipated expiration: 2030-03-25
Also published as: JP5821634B2; EP2412747A4; US9580557B2; WO2010110389A1; EP2412747A1; US20120058333A1; EP2412747B1; JPWO2010110389A1; CN102365315B

Abstract

Provided are: an organo polysiloxane capable of increasing the abrasion resistance and weather resistance of a hard coat layer obtained by using said organo polysiloxane in a silicone hard coating composite; a hard coating composite capable of forming, on the surface of a resin substrate, a hard coat layer having excellent abrasion resistance and weather resistance; a resin substrate having a hard coat layer with excellent abrasion resistance and weather resistance; and a resin substrate having a hard coat layer that can be bent. The hard coating composite contains (a) an organo polysiloxane having T-units as the primary silicon units, and (b) two types of the same; (a) is an organo polysiloxane having a specific proportion of three types of T-unit, and (b) is an organo polysiloxane with a weight-average molecular weight between 1/10and 1/1.5 that of (a). The provided organo polysiloxane is (a), and also provided is a resin substrate having the abovementioned composite, cured, as a hard coat layer.

Description

Organopolysiloxane and hard coating material composition and resin substrate with hard coat

Technical field

The present invention relates to organopolysiloxane and the resin substrate that contains the hard coating material composition of this organopolysiloxane and have the hard coat that uses this hard coating material composition and obtain.

Background technology

In recent years, as for motor vehicle window glasss such as automobiles, be installed on the window glass that the building materials of buildingss such as house, building are used, replace the unorganic glass plate that uses so far, to the upswing in demand of transparent resin plate.Especially; For vehicles such as automobiles; The scheme of window material has been proposed transparent resin plate is used for for lightweight; Especially, the transparent resin plate of aromatic copolycarbonate system is owing to excellences such as anti-destructiveness, the transparency, light weight, workability have been studied its use as promising vehicle window material.In addition, in the roof of communal facility etc., balcony, bicycle shed, arcade, building materials purposes such as light transmission soundproof wall at super expressway, its demand is also enlarging.Yet this transparent resin plate has problems aspect scuff resistance, weathering resistance when replacing sheet glass to use.Therefore, for scuff resistance and the weathering resistance that improves transparent resin plate, proposed to use the hard paint of various hard paint, particularly silicon-types on the surface of transparent resin plate, to form the scheme of overlay film.

As the example of this scheme, put down in writing following technology in the patent documentation 1: inorganic layer is set at resin glass on polymeric substrate, clips the hard coat that this inorganic layer setting contains organoalkoxysilane.In addition, put down in writing the technology of the coating agent composition that contains organopolysiloxane resins in the patent documentation 2 with (methyl) vinylformic acid functionality substituting group and silanol group.

Above technology is and the relevant technology of silicon-type hard coat that can give scuff resistance and weathering resistance through formation on transparent resin plate; The technology of patent documentation 1 is to improve the technology of the cementability of hard coat; In addition; The technology of patent documentation 2 is technology of improving as the storage stability (weathering resistance) of coating agent composition, rather than improves the scuff resistance of the silicon-type hard coat of seeking further to improve performance and the technology of weathering resistance.

On the other hand; The transparent resin plate of using for above-mentioned building materials; Enforcement be called as cold-forming (cold forming) pressure bending machining at normal temperatures, also increasing in the purposes of using (below be called " the crooked use ") this type under the state of bending, in this purposes, also seek to show excellent properties that solvent resistance, chemical-resistant etc. bring by the characteristic of hard coat film, further improve with above-mentioned compared with techniques performance.And, studied use have the scuff resistance that possesses to a certain degree, the resin substrate of the silicon-type hard coat of weathering resistance.Yet; Resin substrate with silicon-type hard coat does not have the crooked patience of the pressure under the normal temperature; Existing can be because the set of the generation of the crackle on the hard coat film, the fine crack on the resin substrate (crazing, generation crazing) etc. and the problem that the transparency lacks, hard coat film is peeled off, physical strength reduces takes place.

For the resin substrate that will have the silicon-type hard coat that possesses weathering resistance is used for crooked purposes or three-dimensional processing article; The resin substrate that need coat prebends processes, or use resin substrate with thermoformable silicon-type hard coat; But hard coat film self is extremely responsive for thermal stresses and stress in bending, and situation about after the moulding article are cooled to room temperature, cracking is more.

In order to address this problem, put down in writing the technology of method of manufacture of the thermoplastic article of flexible organosilicon coating that plastic substrate uses and thermoformable wear resistant in the patent documentation 3, but not about forcing the concrete record of bending machining.

Therefore; Seek to develop a kind of resin substrate with silicon-type hard coat; This hard coat has can be to giving sufficient scuff resistance and weathering resistance by the transparent resin substrate that constitutes as various window materials, the promising polycarbonate-based resin of vehicle window material etc., and can the long term maintenance transparency, its excellent characteristic such as anti-destructiveness; And then, also seek to develop a kind of resin substrate with the crooked silicon-type hard coat that uses of ability, this hard coat also has the splitting resistance that the mechanical stress of receiving is done the time spent on the basis of scuff resistance, weathering resistance.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-313804 communique

Patent documentation 2: japanese kokai publication hei 10-30068 communique

Patent documentation 3: japanese kokai publication hei 2-150430 communique

Summary of the invention

The problem that invention will solve

The present invention makes for the problem that solves above-mentioned prior art and have, its purpose be to provide can be through in the silicon-type hard coating material composition, using its scuff resistance that improves the gained hard coat and weathering resistance organopolysiloxane and can the hard coating material composition of the hard coat that forms scuff resistance on the resin substrate surface and have excellent weather resistance and have scuff resistance and the resin substrate of the hard coat that has excellent weather resistance and having on the basis of scuff resistance, weathering resistance, also possess the mechanical stress of receiving do the time spent splitting resistance can crooked use the resin substrate of silicon-type hard coat.

The scheme that is used to deal with problems

Organopolysiloxane of the present invention is characterised in that; It presses the proportional meter of unit number; Ratio with T1: T2: T3=0～5: 15～40: 55～85 and T3/T2=1.5～4.0 contains the linkage containing silicon unit shown in following T1～T3; The intramolecular number (B) that is bonded to the hydroxyl of Siliciumatom is on average counted more than 12.0 by molecule with the ratio (B)/(A) that is bonded to the number (A) of the alkoxyl group of Siliciumatom, and the matter average molecular weight is 800～8000

T1：R-Si(-OX) ₂(-O ^*-)

T2：R-Si(-OX)(-O ^*-) ₂

T3：R-Si(-O ^*-) ₃

In the formula, R representes the replacement or the unsubstituted any monovalent organic radical group of Wasserstoffatoms or carbon number 1～10, and X representes the alkyl of Wasserstoffatoms or carbon number 1～6, O ^*Expression connects the Sauerstoffatom of 2 Siliciumatoms.

In addition; Hard coating material composition of the present invention is characterised in that; It contains and has the unitary organopolysiloxane of the linkage containing silicon shown in following T1～T3 (a) and have the unitary organopolysiloxane of the linkage containing silicon shown in following T1～T3 (b); Said organopolysiloxane (a) is the organopolysiloxane of the invention described above, and said organopolysiloxane (b) is the organopolysiloxane of 1/10～1/1.5 times matter average molecular weight with matter average molecular weight of said organopolysiloxane (a)

T1：R-Si(-OX) ₂(-O ^*-)

T2：R-Si(-OX)(-O ^*-) ₂

T3：R-Si(-O ^*-) ₃

In addition, the resin substrate with hard coat of the present invention is characterised in that, the hard coat that its at least one mask at resin substrate has the cured article by the hard coating material composition of the invention described above to constitute.

The effect of invention

Organopolysiloxane of the present invention can be combined in through the organopolysiloxane with other ad hoc structures and use scuff resistance and the weathering resistance that improves the gained hard coat in the silicon-type hard coating material composition.According to hard coating material composition of the present invention; Can on the resin substrate surface, form scuff resistance and the hard coat that has excellent weather resistance; And then, can be formed on also have on the basis of scuff resistance and weathering resistance receiving mechanical stress do the time spent splitting resistance, can the crooked hard coat that uses.In addition, the resin substrate with hard coat of the present invention has excellent scuff resistance and weathering resistance.

Description of drawings

Fig. 1 is the overview of the anchor clamps that when the resin substrate with hard coat is forced pliability test, use.

Description of reference numerals

1 ... Force the pliability test anchor clamps, 2 ... Test film, 3 ... Resin substrate, 4 ... Hard coat film, L ... Regular length (mm)

Embodiment

Embodiment of the present invention below is described.

Organopolysiloxane of the present invention (below be called organopolysiloxane (a)) and after state other organopolysiloxanes of using with organopolysiloxane combination of the present invention in the hard coating material composition, be that organopolysiloxane (b) is mainly by the organopolysiloxane that is called as the solidified nature that the unitary linkage containing silicon of T unit constitutes.

[organopolysiloxane]

Generally, organopolysiloxane constitutes by being called as M unit, D unit, T unit, the unitary linkage containing silicon of Q unit.Wherein, the organopolysiloxane of solidified nature is the polymkeric substance of the oligopolymer shape that mainly is made up of T unit or Q unit, the polymkeric substance that the polymkeric substance that only is made up of the T unit, the polymkeric substance that only is made up of the Q unit is arranged, be made up of T unit and Q unit.In addition, these polymkeric substance also contain a spot of M unit, D unit sometimes.

Generally; In the organopolysiloxane of solidified nature, the T unit is to have 1 Siliciumatom and have 1 Wasserstoffatoms or any monovalent organic radical group and 3 unit that are bonded to the Sauerstoffatom (maybe can be bonded to the functional group of other Siliciumatoms) of other Siliciumatoms that are bonded to this Siliciumatom.Any monovalent organic radical group that is bonded to Siliciumatom is that the atom that is bonded to Siliciumatom is any monovalent organic radical group of carbon atom.The functional group that can be bonded to other Siliciumatoms is hydroxyl or the group (below be called hydrolization group) that forms hydroxyl through hydrolysis.The Sauerstoffatom that is bonded to other Siliciumatoms adds up to 3 with the functional group that can be bonded to other Siliciumatoms; Different according to the quantity of Sauerstoffatom that is bonded to other Siliciumatoms and the functional group that can be bonded to other Siliciumatoms, the T unit is categorized as three kinds of unit that are called as T1, T2, T3.The quantity of the Sauerstoffatom that is bonded to other Siliciumatoms of T1 is 1, and this oxygen atomicity of T2 is 2, and this oxygen atomicity of T3 is 3.In this specification sheets etc., use O ^*Expression is bonded to the Sauerstoffatom of other Siliciumatoms, representes to be bonded to the monovalence functional group of other Siliciumatoms with Z.

In addition, expression is bonded to the O of the Sauerstoffatom of other Siliciumatoms ^*Being the Sauerstoffatom of bonding between 2 Siliciumatoms, is the Sauerstoffatom in the key of representing with Si-O-Si.Therefore, O ^*Between 2 unitary Siliciumatoms of linkage containing silicon, there is 1.In other words, O ^*Represent 2 unitary 2 Sauerstoffatoms that Siliciumatom is common of linkage containing silicon.After in the unitary chemical formula of linkage containing silicon stated, though with O ^*The mode that is bonded to 1 Siliciumatom shows, but this O ^*Be the Sauerstoffatom total, and do not mean that 2 linkage containing silicon unit are to use Si-O with the unitary Siliciumatom of other linkage containing silicons ^*-O ^*The key bonding that-Si representes.

Aforementioned M unit is to have 3 above-mentioned organic groups and 1 O ^*The unit, the D unit is to have 2 above-mentioned organic groups and 2 O ^*(or 1 O ^*With 1 Z group) the unit, the Q unit is to have 0 above-mentioned organic group and 4 O ^*(or 1～3 O ^*With 4 altogether of 3～1 Z groups) the unit.Each linkage containing silicon unit is by not having the Sauerstoffatom (O that is bonded to other Siliciumatoms ^*) compound (below be also referred to as monomer) of (only having the Z group) forms.Below will form the unitary monomer of T and be called the T monomer.Equally also will form M unit, D unit, the unitary monomer of Q and be called M monomer, D monomer, Q monomer.

Monomer usefulness (R '-) _aSi (Z) _4-aExpression.Wherein, a representes 0～3 integer, R ' expression Wasserstoffatoms or any monovalent organic radical group, and Z representes that hydroxyl maybe can be bonded to the monovalence functional group of other Siliciumatoms.In this chemical formula, the compound of a=3 is the M monomer, and the compound of a=2 is the D monomer, and the compound of a=1 is the T monomer, and the compound of a=0 is the Q monomer.In monomer, the Z group is hydrolization group normally.In addition, when R ' exists 2 or 3 (a be 2 or 3 o'clock), a plurality of R ' can be different.As R ', with after to state preferred R be that the group of identical category is preferred.

Curable organopolysiloxane is through converting monomeric a part of Z group into O ^*Reaction obtain.When containing more than 2 kinds the unitary multipolymer of linkage containing silicon, usually, these multipolymers are obtained by each corresponding monomeric mixture at organopolysiloxane.When monomeric Z group was hydrolization group, the Z group converted hydroxyl into through hydrolysis reaction, and then, through the dehydration condensation between 2 hydroxyls that are bonded to different Siliciumatoms, 2 Siliciumatoms are via Sauerstoffatom (O ^*) bonding.Residual in the curable organopolysiloxane have a hydroxyl (or unhydrolysed Z group), when curable organopolysiloxane solidifies, and these hydroxyls, Z group and above-mentioned likewise reaction the and solidify.The cured article of curable organopolysiloxane is the three-dimensional cross-linked polymkeric substance that forms, and the cured article of T unit, Q unit curable organopolysiloxane how is the high cured article of cross-linking density.Can think that during curing, the Z group of curable organopolysiloxane is converted into O ^*, but a part of Z group (particularly hydroxyl) is residual, forms the cured article with hydroxyl.When curable organopolysiloxane was solidified, forming hydroxyl did not sometimes have residual cured article basically yet.

When monomeric Z group is hydrolization group,, can enumerate out alkoxyl group, chlorine atom, acyloxy, NCO etc. as this Z group.As a rule, use the monomer of Z group as monomer as alkoxyl group.Alkoxyl group is to compare reactive lower hydrolization group with chlorine atom etc., and in the curable organopolysiloxane that the monomer that uses the Z group as alkoxyl group obtains, unreacted alkoxyl group is more as the situation of Z group existence with hydroxyl.When monomeric Z group is reactive higher hydrolization group (for example chlorine atom), use this monomer and its major part of Z group in the curable organopolysiloxane that obtains is hydroxyl.Therefore, in common curable organopolysiloxane, constitute that Z group in its each unit is made up of hydroxyl or situation about constituting by hydroxyl and alkoxyl group more.

[organopolysiloxane of the present invention]

Organopolysiloxane of the present invention (a), organopolysiloxane (b) are above-mentioned curable organopolysiloxanes.Below under the situation that is not having to specify, abbreviate the organopolysiloxane of solidified nature as organopolysiloxane.

Organopolysiloxane of the present invention (a), organopolysiloxane (b) are the polymkeric substance that mainly is made up of the T unit, also can be except the T unit, also to contain a small amount of other unitary polymkeric substance.As other unit, D unit and Q unit are preferred, and the Q unit is preferred especially.Organopolysiloxane of the present invention (a), organopolysiloxane (b) are the T unit number with respect to the ratio of M unit, D unit, T unit and the unitary sum of Q is 50～100% organopolysiloxane; This ratio is that 70～100% organopolysiloxane is preferred, and this ratio is that 90～100% organopolysiloxane is preferred.And then as organopolysiloxane (a), the unitary ratio of T is that 95～100% organopolysiloxane is preferred especially.Through making the unitary ratio of T high, can obtain the cured article of target.The ratio of M unit, D unit, T unit, the unitary quantity of Q can according to by ²⁹The value of the peak area ratio that Si-NMR obtains is calculated.

Organopolysiloxane (a) as organopolysiloxane of the present invention is to have the unitary organopolysiloxane of the T shown in following T1～T3.Organopolysiloxane (b) also is to have the unitary organopolysiloxane of the T shown in following T1～T3.

T1：R-Si(-OX) ₂(-O ^*-)

T2：R-Si(-OX)(-O ^*-) ₂

T3：R-Si(-O ^*-) ₃

(in the formula, R representes the replacement or the unsubstituted any monovalent organic radical group of Wasserstoffatoms or carbon number 1～10, and X representes the alkyl of Wasserstoffatoms or carbon number 1～6, O ^*Expression connects the Sauerstoffatom of 2 Siliciumatoms.)

R in the above-mentioned chemical formula is not limited to a kind of, and T1, T2, T3 can contain multiple R respectively.In addition, in the above-mentioned chemical formula-OX representes hydroxyl or alkoxyl group.-OX can be the same or different between T1 and T2.2-OX among the T1 can be different, for example, can one are hydroxyls, another is alkoxyl group.In addition, 2-when OX was alkoxyl group, these alkoxyl groups can be different alkoxyl groups.But, be described below, common 2 alkoxyl groups are identical alkoxyl groups.In addition, organopolysiloxane (a) is mutually different organopolysiloxane with organopolysiloxane (b), the R in the above-mentioned chemical formula ,-OX can be different between two organopolysiloxanes.

Sauerstoffatom (the O that below will not have in addition, 2 Siliciumatoms of bonding ^*), the T unit that only has 3 a-OX is called T0.In fact T0 is equivalent to the unreacted T monomer that contains in the organopolysiloxane, is not the linkage containing silicon unit.This T0 likewise measures with T1～T3 in the unitary analysis of T1～T3.

T0～T3 in the organopolysiloxane can pass through nuclear magnetic resonance spectroscopy ( ²⁹Si-NMR) the bonding state of measuring the Siliciumatom in the organopolysiloxane is resolved.The ratio of the quantity of T0～T3 by ²⁹The peak area of Si-NMR is recently obtained.In the organopolysiloxane molecule-OX can resolve through infrared absorption analysis.The hydroxyl that is bonded to Siliciumatom is recently obtained by the peak area of both infrared absorption peaks with the ratio of the quantity of alkoxyl group.Matter average molecular weight Mw, number-average molecular weight Mn and the dispersity Mw/Mn of organopolysiloxane is meant that through GPC be the value that reference material records with the PS.The characteristic of this organopolysiloxane is not meant the characteristic of 1 molecule, but the average characteristics of each molecule of obtaining.

In organopolysiloxane (a), organopolysiloxane (b), a plurality of T1 that exist in 1 molecule, T2, T3 can exist different two or more respectively.For example, can there be the different two or more T2 of R.This organopolysiloxane is obtained by the monomeric mixture of two or more T.For example, can think and in the organopolysiloxane that the two or more Ts monomeric mixture different by R obtains, have R different each two or more T1, T2, T3.The ratio of the quantity of the different R in the organopolysiloxane that is obtained by the different monomeric mixture of multiple T of R has reflected the ratio of components as the T monomer mixtures T whole unit, that R is different.Yet the ratio of the unitary quantity that T1, T2, the T3 R in separately is different might not reflect the ratio of components of the T monomer mixture that R is different.Its reason is, even 3-OX in the T unit is identical, but the reactivity of T monomer, T1, T2 can be different because of R sometimes.

Organopolysiloxane (a) and organopolysiloxane (b) are preferably by with R-Si (OY) ₃At least a manufacturing the in the T monomer of expression.In this formula, R is identical with above-mentioned R, and Y representes the alkyl of carbon number 1～6.Y can also be substituted alkyls such as alkoxyl group substituted alkyl except unsubstituted alkyl.3 Y in 1 molecule can be different.Yet common 3 Y are identical alkyl.Y is preferably the alkyl of carbon number 1～4, and more preferably carbon number is 1 or 2.As concrete Y, can enumerate out methyl, ethyl, n-propyl, normal-butyl, the tertiary butyl, 2-methoxy ethyl etc.

R is the replacement or the unsubstituted any monovalent organic radical group of Wasserstoffatoms or carbon number 1～10.Organic group is meant that as previously mentioned the atom that is bonded to Siliciumatom is the organic group of carbon atom.

As unsubstituted any monovalent organic radical group, can enumerate out alkyl such as alkyl, thiazolinyl, alkynyl, naphthenic base, aryl, aralkyl.As these alkyl, the alkyl of preferred carbon number 1～10, the thiazolinyl of carbon number 2～10, alkynyl, carbon number 5 or 6 naphthenic base, the aryl of carbon number 6～10, or the aralkyl of carbon number 7～10.Particularly, can enumerate out methyl, ethyl, n-propyl, normal-butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, decyl, vinyl, allyl group, cyclohexyl, phenyl, benzyl, styroyl etc.

As substituted any monovalent organic radical group, ring hydrogen atoms such as naphthenic base, aryl, aralkyl are arranged by alkyl substituted alkyl, replacement organic group that the Wasserstoffatoms of aforementioned alkyl has been replaced by halogen atom, functional group, the organic group etc. that contains functional group etc.As functional group, hydroxyl, sulfydryl, carboxyl, epoxy group(ing), amino, cyanic acid etc. are preferred.Replace organic group as halogen atom, the alkyl that chlorine alkyl, Polyfluoroalkyl etc. have chlorine atom or fluorine atom is preferred.As containing functional group's organic group, alkoxyl group, acyl group, acyloxy, alkoxy carbonyl, glycidyl, epoxycyclohexyl, alkylamino, dialkyl amido, arylamino, N-aminoalkyl group substituted-amino alkyl etc. are preferred.Especially, chlorine atom, sulfydryl, epoxy group(ing), amino, acryloxy, methacryloxy, glycidyl, alkylamino, N-aminoalkyl group substituted-amino alkyl etc. are preferred.The T monomer that have by functional group, contains the replacement organic group that functional group's organic group etc. replaced comprises the compound of the category that is called as silane coupling agent.

As the object lesson that replaces organic group; Can enumerate out following organic group: 3-chloropropyl, 3; 3; 3-trifluoro propyl, 3-sulfydryl propyl group, to mercapto methyl phenylethyl, 3-acryloxy propyl group, 3-methacryloxypropyl, 3-glycidoxy propyl group, 2-(3, the 4-epoxycyclohexyl) ethyl, 3-aminopropyl, N-phenyl-3-aminopropyl, N-(2-amino-ethyl)-3-aminopropyl, 2-cyano ethyl.

As the preferred especially any monovalent organic radical group of above-mentioned R is the alkyl of carbon number 1～4.As organopolysiloxane (a) and organopolysiloxane (b), use the T of alkyl with carbon number 1～4 monomeric one or more and the organopolysiloxane that obtains is preferred.In addition, as organopolysiloxane (a) and organopolysiloxane (b), it also is preferred using the monomeric organopolysiloxane that more than one obtain with a small amount of other T monomers of T of the alkyl with carbon number 1～4.The monomeric ratio of other T is preferably 30 moles below the % with respect to T monomer total amount, is preferably 15 moles especially below the %.As other T monomers, be called as silane coupling agent category, have by functional group, the T monomer that contains the replacement organic group that functional group's organic group etc. replaced is preferred.

As the monomeric object lesson of the T of alkyl, for example can enumerate out methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane with carbon number 1～4.Especially, methyltrimethoxy silane or ethyl trimethoxy silane are preferred.As having the monomeric object lesson of T that replaces organic group etc., for example can enumerate out following compound:

Vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3; 3; 3-trifluoro propyl Trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane, 3-TSL 8330,3-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330,3-cyano ethyl Trimethoxy silane.

As except (OY) with R-Si ₃Usefulness beyond the T monomer of expression (R '-) _aSi (Z) _4-aThe T monomer (a=3) of expression for example can be enumerated out METHYL TRICHLORO SILANE, ethyl trichlorosilane, phenyl-trichloro-silicane, 3-glycidoxy propyltrichlorosilan, methyl triacetoxysilane, ethyl triacetoxysilane etc.

With (R '-) _aSi (Z) _4-aIn the D monomer (a=2) of expression, 2 R ' can be the same or different.Under identical situation, the alkyl of carbon number 1～4 is preferred.Under condition of different, a R ' is the alkyl of carbon number 1～4, and another R ' is preferably the replacement organic group that has been replaced by aforementioned functional groups, the organic group etc. that contains functional group.In addition, as the Z group, the alkoxyl group of carbon number 1～4, acetoxyl group etc. are preferred.As the D monomer, for example can enumerate out following compound:

Dimethyldimethoxysil,ne, dimethyldiethoxysilane, vinyl methyl dimethoxysilane, vinyl methyldiethoxysilane, phenyl methyl dimethoxy silane, phenyl methyl diacetoxy silane, 3-chloropropylmethyldimethoxysilane, 3; 3,3-trifluoro propyl methyl dimethoxysilane, 3-sulfydryl propyl group methyldiethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl methyldiethoxysilane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-cyano ethyl methyl dimethoxysilane.

With (R '-) _aSi (Z) _4-aIn the Q monomer (a=0) of expression, 4 Z groups can be different, but are generally identical.As the Z group, the alkoxyl group of carbon number 1～4 is preferred, and methoxy or ethoxy is preferred especially.As the Q monomer, for example can enumerate out following compound:

Tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, four n-butoxy silane, four sec.-butoxy silane, four tert.-butoxy silane.

Organopolysiloxane of the present invention obtains through making partly hydrolysed condensations such as above-mentioned T monomer.Usually, through being heated in solvent with water, T monomer etc. carries out this reaction.Preferably there is catalyzer in the reaction system.Reaction conditionss such as the kind of amount that can be through regulating monomeric kind, water, Heating temperature, catalyzer, the amount of catalyzer, reaction times come the organopolysiloxane of manufacturing objective.In addition, according to circumstances, can use commercially available organopolysiloxane to come the organopolysiloxane of manufacturing objective.In addition, under the situation of organopolysiloxane of the present invention (b), can also directly use corresponding commercially available organopolysiloxane.

As above-mentioned catalyzer, acid catalyst is preferred.As acid catalyst, can enumerate out mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, thionamic acid; Organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succsinic acid, toxilic acid, lactic acid, tosic acid.Acetic acid is preferred especially.As above-mentioned solvent, hydrophilic organic solvent is preferred, and pure series solvent is preferred especially.As pure series solvent, can enumerate out methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, cellosolvo, 4-methyl-2-amylalcohol, butoxy ethanol etc.For temperature of reaction,, can at room temperature react existing under the situation of catalyzer.Usually, from 20～80 ℃ temperature of reaction, adopt suitable temperature according to purpose.

Hydrolysis-condensation reaction is the reaction that generates T3 by T0 (T monomer) generation T1, by T1 generation T2, by T2.Can think that the speed of response of condensation reaction is slack-off successively by following order: generate the condensation reaction of T1 by the T0 that is converted into hydroxyl more than 1 of hydrolization group; By among the 2-OX at least one is the condensation reaction that the T1 of hydroxyl generates T2, is the condensation reaction that the T2 of hydroxyl generates T3 by-OX.Even consider the hydrolysis reaction of hydrolization group, can think that also the peak along with each unitary amount of carrying out of reaction moves to T3 from T0.When reaction conditions is gentle, can think that the moving of peak of amount carried out more in an orderly manner.On the other hand, when reaction conditions was relatively fierce, reaction was carried out randomly, each unitary amount be scattered in tabular, with respect to the amount of T2, T3, the amount of T0, T1 is easy to increase.Be described below; Organopolysiloxane of the present invention (a) is the less and T2 of the amount of T0, T1 and the organopolysiloxane of the ratio of the amount of T3 at the higher molecular weight of specified range, and this organopolysiloxane can be made through selecting relatively mild reaction conditions.

The reactivity of above-mentioned condensation reaction changes according to R, R not simultaneously, the reactivity of hydroxyl also changes.Usually, R more little (for example the carbon number of alkyl is few more when R is alkyl), the reactivity of hydroxyl is high more.Therefore, consider that preferably the reactivity of hydrolization group and reactive relation of hydroxyl select the T monomer.

In addition, the speed that hydrolization group converts the hydrolysis reaction of hydroxyl into can change according to the kind of hydrolization group, the relation of the speed of preferred consideration and condensation reaction.For example, be under the situation of alkoxyl group at the OX of T2 group, the speed of its hydrolysis reaction is crossed when slow, and the OX group is that the T2 of hydroxyl reduces.Likewise, the speed of hydrolysis reaction is crossed when slow, and the OX group is that the T1 of hydroxyl reduces.Therefore, become and be difficult to obtain hydroxyl in the organopolysiloxane with respect to the high material of ratio of the amount of alkoxyl group.Therefore, as the high alkoxyl group of the alkoxyl group preferred reactive of OX group, the promptly preferred few alkoxyl group of carbon number, most preferably methoxyl group.When hydrolization group reactive enough high, less carry out condensation reaction by the high organopolysiloxane of the ratio of hydrolization group, can obtain the high organopolysiloxane of hydroxyl ratio.

[organopolysiloxane (a)]

Each unit that contains T1～T3 as the organopolysiloxane (a) of organopolysiloxane of the present invention with the ratio of T1: T2: T3=0～5: 15～40: 55～85 and T3/T2=1.5～4.0.In addition, about the OX group in the organopolysiloxane (a), the OX group is that the OX group is the ratio (B)/(A) on average count more than 12.0 by molecule of number (A) of number (B) and the alkoxyl group of hydroxyl.And the matter average molecular weight of organopolysiloxane (a) is 800～8000.In addition, organopolysiloxane (a) is substantially free of the monomeric T0 as T.

About the ratio of the T1, T2 and the T3 that constitute organopolysiloxane (a), preferably, on the basis of above-mentioned condition, (T2+T3)/(T1+T2+T3) in 0.85～1.00 scope, more preferably more than 0.90 and be lower than 1.00.In addition, about T3/T2, preferred range is 2.0～4.0.

The ratio that makes the T1, T2 and the T3 that constitute organopolysiloxane (a) through the average composition with each molecule is in this scope; Thereby; With organopolysiloxane (a) with after organopolysiloxane (b) combination stated and when being used for hard coating material composition of the present invention, can improve the scuff resistance and the weathering resistance of gained hard coat.

(B)/(A) in the organopolysiloxane (a) is the parameter of expression condensation reaction property; This value is big more; The ratio of promptly comparing hydroxyl with alkoxyl group is big more, the curing reaction in the time of then when organopolysiloxane (a) is formed hard coating material composition with organopolysiloxane (b) combination, promoting more to form hard coat.In addition, the worry that unreacted when forming hard coat and residual alkoxyl group have the scuff resistance that causes hard coat to reduce if after fixing carries out, then also can become the reason of tiny crack, and the ratio of therefore comparing hydroxyl with alkoxyl group is high more good more.(B)/(A) in the organopolysiloxane (a) more than 12.0, is preferably more than 16.0.In addition, (A) can be 0.

(B)/(A) value was less than 12.0 o'clock, and the ratio of comparing hydroxyl with alkoxyl group is very few, can't obtain to promote the effect of curing reaction, in addition, the worry that has the influence owing to alkoxyl group to cause scuff resistance to reduce, after fixing carries out and becomes the reason of tiny crack.Promptly; (B)/(A) value was less than 12.0 o'clock; When forming hard coat; Be not easy to ooze out etc. owing to a part of organopolysiloxane (a) is imported into to become in the three-dimensional crosslinking structure (network) that the curing reaction by organopolysiloxane (a) and organopolysiloxane (b) forms, therefore can produce cross-linking density and reduce, can't obtain problems such as wear resistant, curing are difficult to fully carry out.

The matter average molecular weight of organopolysiloxane (a) is 800～8000, is preferably 1000～6000.Matter average molecular weight through making organopolysiloxane (a) when organopolysiloxane (a) is used for hard coating material composition of the present invention with organopolysiloxane (b) combination, can fully improve the scuff resistance and the weathering resistance of gained hard coat in this scope.

In the present invention; In particular for obtaining the organopolysiloxane of the present invention (a) that in the hard coating material composition of the hard coat that is used to form excellent scratch resistance, uses; Water-disintegrable silane compound as raw material; Be methyl trialkoxysilane more than the preferred 70 quality % that use in whole T monomers, more preferably the carbon number of alkoxyl group is 1～4.But, in order to improve functions such as adaptation, performance wetting ability, water repellency, also can make up and use a spot of T monomer except methyl trialkoxysilane.

As the method for making organopolysiloxane (a), as stated, in solvent, in the presence of acid catalyst, make the monomer condensation reaction that is hydrolyzed.Here, for the required water of hydrolysis, with respect to 1 equivalent monomer, water is 1～10 equivalent usually, is preferably 1.5 equivalents～7 equivalents, further is preferably 3～5 equivalents.With monomer hydrolysis and condensation the time, also can in the reaction system that has colloidal silica (afterwards stating), carry out, during as this colloidal silica, water is supplied with by this dispersion liquid at the colloidal silica that uses aqueous dispersion type.The consumption of acid catalyst is preferably 0.1～50 mass parts with respect to 100 mass parts monomers, is preferably 1～20 mass parts especially.As solvent, aforementioned pure series solvent is preferred, and from the viewpoint of the favorable solubility of gained organopolysiloxane (a), particularly, methyl alcohol, ethanol, 2-propyl alcohol, 1-butanols or 2-butanols are preferred especially.

Usually, temperature of reaction adopts 20～40 ℃, and the reaction times is adopted 1 hour～a couple of days.Monomeric hydrolysis-condensation reaction is thermopositive reaction, but the temperature of preferred system is no more than 60 ℃.Hydrolysis reaction is fully carried out, then stable in order to make the gained organopolysiloxane, also preferably under 40～80 ℃, carry out the condensation reaction of 1 hour～a couple of days.

Organopolysiloxane (a) can also be made by commercially available organopolysiloxane.Because the commercially available organopolysiloxane normally ratio of alkoxyl group is higher than the organopolysiloxane of hydroxyl; Therefore particularly preferably be; Use except above-mentioned (B)/(A) with the similar commercially available organopolysiloxane of organopolysiloxane (a) of target; Improve the ratio of hydroxyl with hydrolysis reaction, thereby make organopolysiloxane (a).

As the commercially available organopolysiloxane of the raw material that can be used as organopolysiloxane (a), the following organopolysiloxane as the partly hydrolysed condenses of methyltrimethoxy silane is for example arranged.In addition, " ND " this record is represented, measures at the magnetic nuclear resonance analyzer ECP400 (trade(brand)name) that uses NEC's manufactured ²⁹During the peak area ratio of Si-NMR (following same) below the detection limit.

Methyl is silicone resin KR-220L (trade(brand)name, chemical industrial company of SHIN-ETSU HANTOTAI makes); T0: T1: T2: T3=ND: ND: 28: 72, Si-OH/SiO-CH ₃=11.7, matter average molecular weight Mw=4720, number-average molecular weight Mn=1200, Mw/Mn=3.93.

Methyl is silicone resin KR-500 (trade(brand)name, chemical industrial company of SHIN-ETSU HANTOTAI makes); T0: T1: T2: T3=ND: 15: 58: 27, unconfirmed through FT-IR to the peak that derives from the Si-OH group, basically only there is SiO-CH ₃Mw＝1240，Mn＝700，Mw/Mn＝1.77。

When making organopolysiloxane (a), preferably in the presence of acid catalyst, mainly commercially available organopolysiloxane is carried out the hydrolysis of alkoxyl group by aforesaid commercially available organopolysiloxane.For example can enumerate out following method etc.: the solvent that in commercially available organopolysiloxane, adds 0～10 times of amount (quality); Fully stir; Then add the aqueous acid of 0.1～70 quality % left and right sides concentration, 15～80 ℃, preferably under 20～70 ℃ temperature, stirred 1～24 hour.As employed solvent, can use water solvent, can use the aforementioned pure series solvent that is added with water in addition.

[organopolysiloxane (b)]

Hard coating material composition of the present invention contains organopolysiloxane (a) and organopolysiloxane (b).Organopolysiloxane (b) is the organopolysiloxane of 1/10～1/1.5 times matter average molecular weight with matter average molecular weight of organopolysiloxane (a).Organopolysiloxane (b) be the matter average molecular weight less than with the organopolysiloxane of the organopolysiloxane (a) of its combination, have aforementioned T1～T3 unit.To the ratio of the quantity of T1, T2, T3, the ratio of T3/T2, not special qualification of ratio of (B)/(A).

The matter average molecular weight of organopolysiloxane (b) is preferably 1/8～1/1.5 times with the organopolysiloxane (a) of its combination.When the matter average molecular weight of organopolysiloxane (b) surpasses 1/1.5 times of matter average molecular weight of organopolysiloxane (a); In other words; The matter average molecular weight of organopolysiloxane (a) is during less than 1.5 times of the matter average molecular weight of organopolysiloxane (b); The toughness of gained hard coat reduces, and can become the major cause that cracks.In addition; The matter average molecular weight of organopolysiloxane (b) is during less than 1/10 times of the matter average molecular weight of organopolysiloxane (a); In other words; When the matter average molecular weight of organopolysiloxane (a) surpassed 10 times of matter average molecular weight of organopolysiloxane (b), the scuff resistance of gained hard coat reduced, the hard coat that can't obtain having sufficient scuff resistance.

Preferred organopolysiloxane (b) is each the linkage containing silicon unit shown in T0, T1, T2 and the T3 by the proportional meter of these unit numbers organopolysiloxane in the scope of T0: T1: T2: T3=0～5: 0～50: 5～70: 10～90.The big expression of ratio of T0 in the organopolysiloxane (b) and T1 generally when making this organopolysiloxane hydrolysis reaction, the condensation reaction of starting monomer insufficient.In organopolysiloxane (b), if the ratio of T0 and T1 is big, during thermofixation when the hard coating material composition of the present invention that then contains itself and organopolysiloxane (a) in use forms hard coat, the generation of crackle is tended to increase.In addition, generally when making organopolysiloxane, if the condensation reaction of starting monomer is excessively carried out, then the ratio of the T3 of gained organopolysiloxane increases.In organopolysiloxane (b); If the ratio of T3 increases more than required, during thermofixation when the hard coating material composition of the present invention that then contains itself and organopolysiloxane (a) in use forms hard coat, can become is difficult to carry out the proper crosslinking reaction; Therefore; The worry that can't form hard coat is arranged, in addition, can't obtain having the hard coat of sufficient scuff resistance sometimes.

As organopolysiloxane (b), same with organopolysiloxane (a), can wait by the T monomer and make.In addition, can directly use commercially available organopolysiloxane as organopolysiloxane (b).Commercially available organopolysiloxane as can be used as organopolysiloxane (b) for example has following organopolysiloxane.In addition, " trace " this record is represented, measures at the magnetic nuclear resonance analyzer ECP400 (trade(brand)name) that uses NEC's manufactured ²⁹Be more than 0.01 during the peak area ratio of Si-NMR and 0.25 below (following same).

トスガ one De 510 (trade(brand)name, Momentive Performance Materials Inc. makes); Molecular weight: Mn=1370, Mw=1380, Mw/Mn=1.01.The unitary number of T: (total amount of M unit and D unit and the unitary number separately of Q)=more than 99.9: ND.T0∶T1∶T2∶T3＝ND∶2∶36∶62。

KP851 (trade(brand)name: chemical industrial company of SHIN-ETSU HANTOTAI makes): Mn=1390, Mw=1400, Mw/Mn=1.01, the unitary number of T: (total amount of M unit and D unit and the unitary number separately of Q)=and more than 99.9: ND.T0: T1: T2: T3=trace: 21: 58: 21.

[hard coating material composition]

Hard coating material composition of the present invention contains organopolysiloxane (a) and organopolysiloxane (b).Content as organopolysiloxane in the hard coating material composition of the present invention (a) and organopolysiloxane (b); The matter average molecular weight that depends on each composition; And with respect to the compsn of having deducted solvent (following be called as required " nonvolatile component ") total amount; The content of preferred organopolysiloxane (a) is that the content of 1～35 quality %, organopolysiloxane (b) is 40～65 quality %, and more preferably the content of organopolysiloxane (a) is that the content of 5～25 quality %, organopolysiloxane (b) is 45～65 quality %.In this manual, the amount of nonvolatile component is meant the amount of measuring according to the quality change of the hard coating material composition after 150 ℃ of held 45 minutes.

When the content of the organopolysiloxane in the nonvolatile component in the hard coating material composition of the present invention (a) was lower than 1 quality %, the toughness of gained hard coat reduced, and became sometimes easily owing to life-time service cracks.And aforementioned content is when surpassing 35 quality %, and the hardness of gained hard coat has the tendency of reduction.In addition; When the content of the organopolysiloxane in the nonvolatile component in the hard coating material composition of the present invention (b) is lower than 40 quality %; (a) composition in the nonvolatile component, (b) become the ratio of the organopolysiloxane of subtotaling to become low relatively excessively; The thermofixation that is difficult to through organopolysiloxane that becomes sometimes forms hard coat, or the gained hard coat can crack.On the other hand, when the content of organopolysiloxane (b) surpassed 65 quality %, the toughness of gained hard coat reduced, and became sometimes easily owing to life-time service cracks.

In addition, the above-mentioned organopolysiloxane (b) in the hard coating material composition of the present invention is preferably 1.5～30 times with respect to the ratio of the content of organopolysiloxane (a) by mass ratio, more preferably 2～15 times.Hard coating material composition of the present invention is through containing this two with this ratio; Make the organopolysiloxane three-dimensional crosslinking structure that forms by curing reaction form the structure in the three-dimensional crosslinking structure that (a) composition organopolysiloxane partly imported to organopolysiloxane (b) main body, can make the weathering resistance of gained hard coat and scuff resistance good.

In hard coating material composition of the present invention, except containing above-mentioned organopolysiloxane (a) and the organopolysiloxane (b), can also containing various additives.For example, in order further to improve the scuff resistance of the hard coat of the resin substrate with hard coat of the present invention, the hard coating material composition that contains silicon dioxide microparticle (c) is preferred.Therefore, preferred compounding colloidal silica in hard coating material composition.In addition, colloidal silica is meant that silicon dioxide microparticle is dispersed in the organic solvents such as water or methyl alcohol, ethanol, isopropylcarbinol, propylene glycol monomethyl ether and the material that forms.Can when making hard coating material composition of the present invention, make the hard coating material composition of the present invention that contains silicon dioxide microparticle (c) by suitable compounding colloidal silica.

In addition, silicon dioxide microparticle (c) also can be in the manufacturing processed of above-mentioned organopolysiloxane (a), organopolysiloxane (b) compounding in the monomer of raw material.Through in containing the reaction system of colloidal silica, making organopolysiloxane (a), organopolysiloxane (b), can obtain containing organopolysiloxane (a), the organopolysiloxane (b) of silicon dioxide microparticle (c).For example can in colloidal silica, add T monomer and the water, the acid catalyst that depend on the needs, and in the dispersion medium of colloidal silica, make organopolysiloxane (a), organopolysiloxane (b) as described above.Can use the organopolysiloxane (a), the organopolysiloxane (b) that obtain like this to make the hard coating material composition of the present invention that contains silicon dioxide microparticle (c).

The median size (BET method) of the above-mentioned silicon dioxide microparticle (c) that uses in the hard coating material composition of the present invention is preferably 1～100nm.When median size surpassed 100nm, particle is with the light diffuse-reflectance, so the increase of the mist degree of gained hard coat, and was not preferred on optical quality sometimes.And then median size is preferably 5～40nm especially.This is in order to give the transparency that hard coat keeps hard coat in scuff resistance.In addition, colloidal silica can use any one in aqueous dispersion type and the organic solvent decentralized.The preferred aqueous dispersion type that uses.And then, especially preferably use the colloidal silica that dispersion forms in acidic aqueous solution.In addition, in colloidal silica, can also contain silicon dioxide microparticles such as alumina sol, titanium colloidal sol, cerium oxide sol inanimate matter particulate in addition.

As the content of the silicon dioxide microparticle in the hard coating material composition of the present invention (c),, be preferably the amount of 1～50 quality %, more preferably the amount of 5～40 quality % with respect to the compsn of having deducted solvent (nonvolatile component) total amount.When the content of the silicon dioxide microparticle in the nonvolatile component in the hard coating material composition of the present invention (c) is lower than 1 quality %; The gained hard coat can't be guaranteed sufficient scuff resistance sometimes; When aforementioned content surpasses 50 quality %; The ratio of the organopolysiloxane that meets organo-siloxane (a), organo-siloxane (b) total in the nonvolatile component became low, and following worry is arranged: the thermofixation that is difficult to through organopolysiloxane that becomes forms hard coat; The gained hard coat cracks; The transparency reduction of hard coat takes place between the silicon dioxide microparticle (c) to assemble and make; Deng.

Like this; Content as the above-mentioned organopolysiloxane (a) in the hard coating material composition of the present invention, organopolysiloxane (b) and silicon dioxide microparticle (c); With respect to the total composition of having deducted solvent; The content of preferably said (a) is that the content of 1～35 quality %, said (b) is that the content of 40～65 quality %, said (c) is 1～50 quality %, and the content of more preferably said (a) is that the content of 5～25 quality %, said (b) is that the content of 45～65 quality %, said (c) is 10～40 quality %.If use the hard coating material composition of the content of (a)～(c), then can obtain preferred hard coat aspect chemical proofing, the transparency, scuff resistance and weathering resistance as aforementioned range.

For hard coating material composition of the present invention,, can further contain additives such as skimmer, viscous regulator in order to improve the coating on resin substrate; In order to improve the adaptation with resin substrate, can further contain additives such as adaptation imparting agent; In addition, the smoothness for the coating and the gained that improve on resin substrate are filmed can further contain flow agent as additive.The compounding amount of these additives is with respect to total amount 100 mass parts of organopolysiloxane (a) and organopolysiloxane (b) amount that to be preferably every kind of additive component be 0.01～2 weight part.In addition, hard coating material composition of the present invention can contain dyestuff, pigment, filler etc. in the scope of not damaging the object of the invention.

Hard coating material composition of the present invention can further contain curing catalysts.As curing catalysts, can enumerate out an alkali metal salt such as lithium salts, sodium salt, sylvite of aliphatic carboxylic acid (formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartrate, succsinic acid etc.); Quaternary ammonium salts such as benzyl trimethyl ammonium salt, tetramethyl ammonium, tetraethyl-ammonium salt; Metal alkoxide, the inner complex of aluminium, titanium, cerium etc.; Ammoniumper chlorate, ammonium chloride, ammonium sulfate, sodium-acetate, imidazoles and salt thereof, trifluoromethane sulfonic acid ammonium, two (trifluoromethyl sulfonyl) brooethyl ammonium etc.In addition, the compounding amount of curing catalysts is preferably 0.01～10 mass parts with respect to total amount 100 mass parts of organopolysiloxane (a) and organopolysiloxane (b), more preferably 0.1～5 mass parts.When the content of curing catalysts is less than 0.01 mass parts, be difficult to obtain sufficient curing speed, during more than 10 mass parts, the storage stability of hard coating material composition can reduce sometimes, maybe can produce throw out.

In addition, in order to suppress the resin substrate xanthochromia, hard coating material composition of the present invention preferably further contains UV light absorber.As UV light absorber, can enumerate out the benzophenone series UV light absorber, benzotriazole is that UV light absorber, benzoglyoxaline are that UV light absorber, cyanoacrylate are that UV light absorber, salicylate are that UV light absorber, toluenyl malonic ester are that UV light absorber, triazine are UV light absorber etc.These UV light absorbers can use a kind of, also can two or more combinations be used.In addition, from hard coat film, ooze out, can use UV light absorber with trialkoxysilyl in order to suppress above-mentioned UV light absorber.UV light absorber with trialkoxysilyl is converted into hydroxyl through hydrolysis reaction when the thermofixation that utilizes organopolysiloxane forms hard coat; Then be directed in the hard coat, from hard coat film, ooze out thereby can suppress UV light absorber through dehydration condensation.As this trialkoxysilyl, particularly, can enumerate out trimethoxysilyl, triethoxysilyl etc.The content of the UV light absorber in the hard coating material composition is preferably 0.1～50 mass parts with respect to total amount 100 mass parts of organopolysiloxane (a) and organopolysiloxane (b), is preferably 0.1～30 mass parts especially.

In addition, in the present invention, improve storage stability in order to prevent hard coating material composition gelation at normal temperatures, preferably the pH with hard coating material composition is adjusted to 3.0～6.0, more preferably is adjusted to 4.0～5.5.At pH is under the condition below 2.0 or more than 7.0, and the hydroxyl that is bonded to Siliciumatom is extremely unstable, thereby is inappropriate for preservation.As the method for adjustment pH, can enumerate out the content of interpolation acid, adjustment curing catalysts etc.As acid, can enumerate out mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, thionamic acid; Organic acids such as formic acid, acetic acid, propionic acid, butyric acid, succsinic acid, toxilic acid, lactic acid, tosic acid.

Hard coating material composition of the present invention will be usually preparing as the organopolysiloxane (a) of neccessary composition and organopolysiloxane (b) and as the dissolvings such as various additives of optional member, the form that is dispersed in the solvent.Whole nonvolatile component in the aforementioned hard coating material composition are stably dissolved, are dispersed in the solvent is necessary, and therefore, solvent phase contains the alcohol more than at least 20 quality % for the above-mentioned compsn total amount, preferably contains the above alcohol of 50 quality %.

As the alcohol that uses in this solvent; Methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1-methoxyl group-2-propyl alcohol, cellosolvo, 4-methyl-2-amylalcohol and butoxy ethanol etc. are preferred; In the middle of these; From the aspect of the favorable solubility of organopolysiloxane (a) and organopolysiloxane (b), coating on resin substrate good aspect, boiling point is that 80～160 ℃ alcohol is preferred.Particularly, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 1-methoxyl group-2-propyl alcohol, cellosolvo, 4-methyl-2-amylalcohol or butoxy ethanol are preferred.

In addition, the solvent as using in the hard coating material composition of the present invention also comprises: when making organopolysiloxane (a), organopolysiloxane (b), follow the lower alcohol that hydrolysis produced of starting monomer, for example alkyltrialkoxysilaneand etc.; For the water in the aqueous dispersion type colloidal silica and do not participate in the moisture of hydrolysis reaction; When the colloidal silica of dispersed system with an organic solvent its disperses organic solvent.

In addition, in hard coating material composition of the present invention,, can make up use and can carry out miscible other solvents except that alcohol,, can enumerate out ketones such as acetone, methyl ethyl diketone as this solvent with water/alcohol as the solvent beyond above-mentioned; Ester such as vinyl acetic monomer, isobutyl acetate class; Ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Di Iso Propyl Ether.

The amount of the solvent that in hard coating material composition of the present invention, uses is preferably 50～3000 mass parts with respect to whole nonvolatile component 100 mass parts in the hard coating material composition, more preferably 150～2000 mass parts.

Hard coating material composition of the present invention can be given curing overlay film that its curing is obtained scuff resistance and weathering resistance with excellence through having top illustrated composition.In addition, the curing overlay film that is obtained by this hard coating material composition of the present invention promptly can become useful hard coat as long as on resin substrate, form.

In hard coating material composition of the present invention, on the basis of the evaluation of carrying out usually,, also use tensile stress (σ) that the gained curing overlay film has, in order to descend method to obtain as the index of estimating it.

In this manual; The tensile stress (σ) of the above-mentioned curing overlay film that uses as the index of estimating hard coating material composition particularly is meant: use value and the film thickness value of curing overlay film (after solidifying) of the radius-of-curvature of the silicon chip of the curing overlay film that under 25 ℃ of envrionment temperatures, records through the membrane stress determinator before and after forming, the stress value of calculating through the formula shown in the following formula (1).Wherein, determination step details in an embodiment.

[mathematical expression 1]

σ = \frac{E \cdot h^{2}}{(1 - v) \cdot 6 \cdot R \cdot t} \cdot \cdot \cdot (1)

(in the formula (1); R is with the membrane stress determinator records under 25 ℃ of envrionment temperatures, silicon chip is independent radius-of-curvature (Rb) poor (Rb-Ra) [m] with the radius-of-curvature (Ra) of the silicon chip sample that has curing overlay film on the surface that uses said silicon wafer to manufacture; Said curing overlay film is that the hard coating material composition as determinand is solidified to form under 120 ℃, 1 hour condition, and E/ (1/v) is by the elastic modulus E of silicon chip, the twin shaft Young's modulus that PR v calculates (crystal face (100): 1.805 * 10 ¹¹Pa), h is the thickness [m] of silicon chip, and t is the thickness [m] of curing overlay film.)

Usually; The solvent seasoning that the resin substrate of hard coating material composition that is coated with the organopolysiloxane that contains solidified nature contains with aforementioned hard coating material composition under the temperature condition from normal temperature to the heat-drawn wire that is lower than resin substrate, remove; Heating then, thus make Thermocurable organopolysiloxane thermofixation in the aforementioned hard coating material composition, form curing overlay film and become resin substrate with hard coat.In this curing process; In the Thermocurable organopolysiloxane that in aforementioned hard coating material composition, contains; Its silanol group that has (dehydration condensation takes place Si-OH), form siloxane bond (Si-O-Si-), thus form wear resistant excellent in curing overlay film.

Be used for making hard coating material composition dry with the solidified temperature-rise period, by by the capillary force of the evaporation generation of solvent and the above-mentioned dehydration condensation that in filming, carries out, gel-film (filming) densification, its volume decrement reaches tens of %.Gel-film is not a perfect elastic body, if but it is approximately elastomerics, then when in the face direction of filming is shunk because of curing under by the state of resin substrate constraint, can accumulation strain on the direction in the face of filming.As a result, can in the face of gained curing overlay film, produce tensile stress on the direction.This tensile stress is big more, then curing overlay film be easy to generate crackle more, from peeling off of resin substrate etc.

In this manual, tensile stress is quantized with above-mentioned formula (1), be used to estimate hard coating material composition.Shown in above-mentioned formula (1), the difference R of the radius-of-curvature of the silicon chip before and after the formation curing overlay film is decided by thickness h, the elastic modulus E of silicon chip, the PR v of silicon chip, the thickness t of curing overlay film, the tensile stress (σ) of silicon chip.If in the face of the curing overlay film of the single face that is formed on silicon chip, produce tensile stress (σ) on the direction; Then as can finding out from above-mentioned formula (1); The stress that in the face of curing overlay film, produces on the direction (σ) is big more; The difference R of then aforementioned radius-of-curvature is big more, and promptly the warpage as the silicon chip of the base material of curing overlay film is big more.

Therefore, if measure the thickness t of radius of curvature R b, Ra and the curing overlay film of the silicon chip that forms the curing overlay film front and back, then can obtain the tensile stress (σ) of curing overlay film.In addition; The radius of curvature R a that is formed with the silicon chip of curing overlay film can obtain as follows: the single face at monocrystalline silicon piece under above-mentioned condition of cure forms curing overlay film; Use the membrane stress determinator to scan with laser being formed with on the wafer surface of this curing overlay film; Read Ra according to catoptrical direction, thereby obtain.

The radius of curvature R a that forms the silicon chip behind the above-mentioned curing overlay film can get various values according to the kind of the hard coating material composition that is used to form curing overlay film and condition of cure etc.That is, different according to the kind of the hard coating material composition that is used to form curing overlay film and condition of cure etc., the tensile stress (σ) of the curing overlay film of calculating through aforementioned formula (1) also can be various values.Therefore, be set at certain conditions, can estimate hard coating material composition through the tensile stress (σ) of curing overlay film through condition of cure with curing overlay film.In above-mentioned formula (1),, used 120 ℃, 1 hour as the condition of cure of employed curing overlay film.According to this condition of cure, no matter the kind of hard coating material composition how, thermofixation is all accomplished, and, we can say that most silanol group all disappears, forms siloxane bond through dehydrating condensation that is.

For hard coating material composition of the present invention, tensile stress values is calculated through aforementioned formula (1).The tensile stress (σ) of the curing overlay film that the use said composition obtains is preferably below the 31MPa.If this tensile stress (σ) is a hard coating material composition such below the 31MPa; Then through using it to form the hard coat that is made up of the sclerosis overlay film on surface of resin substrate, the lip-deep hard coat that can fully suppress to be formed on this resin substrate cracks, suppresses hard coat and peels off from resin substrate.As a result, can obtain having the resin substrate of the hard coat that has excellent weather resistance.

Here, for hard coating material composition of the present invention, tensile stress values is calculated through above-mentioned formula (1).When the tensile stress (σ) of the curing overlay film that the use said composition obtains surpassed 31MPa, following worry is arranged: the hard coat that uses this hard coating material composition on the surface of resin substrate, to form can crack, or hard coat can be peeled off from resin substrate.In addition; Under the situation of the formed body of curved shapes such as vehicle window; The resin-formed body that use has a unrelieved stress is during as resin substrate, and following worry is arranged: resin can't tolerate the tensile stress of hard coat, can produce the crackle that is called as crazing (craze) on the resin substrate.In addition, be installed in as vehicle window under the situation on the vehicle at the resin substrate that will have hard coat, when resin substrate became curved because of blast etc., the lip-deep hard coat that is formed on resin substrate became and is easy to crack.The higher limit of above-mentioned tensile stress (σ) is preferably 30MPa, is preferably 28MPa especially.In addition, the lower value as aforementioned tensile stress (σ) is suitably 1MPa, is preferably 10MPa, is preferably 20MPa especially.

[resin substrate with hard coat of the present invention]

Resin substrate with hard coat of the present invention can be made as follows: form on the resin substrate of stating after the hard coating material composition of the invention described above is coated on and film, and solidified nature compound in aforementioned the filming is solidified form hard coat, thereby make.As the coating process of hard coating material composition, not special the qualification can be enumerated out common coating methods such as spraying method, dip coating, flow coat method.Preferably come the viscosity, solid component concentration etc. of suitable adjustment hard coating material composition according to coating method.

Be coated on hard coating material composition on the resin substrate dry under the temperature condition of the heat-drawn wire of normal temperature～be lower than resin substrate usually, remove and desolvate, be heating and curing then.When said thermofixation is reflected in the scope that the thermotolerance of resin substrate do not have problems and carries out with comparatively high temps, can accomplish curing quickly, thus preferred.Yet, for example, having under the situation of methyl as the organopolysiloxane of any monovalent organic radical group in use, the temperature when being heating and curing is more than 250 ℃ the time, methyl can break away from because of thermolysis, thereby not preferred.Therefore,, be preferably 50～200 ℃, be preferably 80～160 ℃ especially, especially be preferably 100～140 ℃ as solidification value.Be preferably 10 minutes set time～4 hours, be preferably 20 minutes especially～3 hours, especially be preferably 30 minutes～2 hours.

The thickness of filming (thickness before solidifying) that on the surface of resin substrate, is coated with hard coating material composition and forms depends on the solid component concentration of compsn.Preferably, consider solid component concentration wait suitably adjust so that the thickness after solidifying in the scope of stipulating.

The thickness that is applied in the hard coat on the resin substrate is preferably more than the 2 μ m and below the 10 μ m being preferably more than the 0.1 μ m under the state after the curing and below the 20 μ m, further being preferably more than the 1 μ m and below the 10 μ m especially.When the thickness of hard coat is too small,, also be difficult to guarantee sufficient scuff resistance even used the hard coat of the hard coating material composition of the invention described above.On the other hand, when the thickness of hard coat is excessive, have to be easy to the worry that cracks, peel off.Therefore, in order to ensure sufficient scuff resistance and suppress crackle, peel off generation, it is above and below the 20 μ m that the thickness of hard coat is preferably 0.1 μ m.

The resin substrate with hard coat of the present invention that obtains like this is because the overlay film that is made up of above-mentioned hard coat has excellent scuff resistance and weathering resistance, therefore as for motor vehicle window glasss such as automobiles, to be installed on the window glass that the building materials of buildingss such as house, building use be useful.

In addition; According to the resin substrate with hard coat of the present invention; Even when through the pressure bending machining at normal temperatures that is called as cold-forming flat curved substrate being become the radius-of-curvature of regulation and under this state, using, promptly when being used for so-called " the crooked use ", also have patience to bending; Can fully suppress the generation of the crackle in the hard coat, the set of the fine crack on the resin substrate (crazing, generation crazing) etc.

That is, the present invention provides flat, can carry out the resin substrate with hard coat that the bending under this normal temperature is used completely.Here, normal temperature generally is meant and do not heat especially or temperature that refrigerative is usual, in this manual, 0～80 ℃ TR roughly is called as " normal temperature ".In addition; As the bending range with resin substrate bending use at normal temperatures of hard coat of the present invention; Can enumerate out to the resin substrate that forms hard coat can force till the bending condition of bending machining at normal temperatures; Particularly, to this resin substrate allow the bending condition more than the radius-of-curvature till.Allow that radius-of-curvature is meant the desired value how many resin substrates can crooked use, and is decided by the kind of the resin that constitutes resin substrate and the thickness of resin substrate here.For example, when resin substrate is made up of polycarbonate resin, allow that radius-of-curvature representes with R=180t (t is the thickness [mm] of resin substrate).

In addition; Crooked when using the resin substrate with hard coat of the present invention as described above; The thickness that is applied in the hard coat on the resin substrate is being preferably more than the 0.1 μ m and below the 6 μ m under the state after the curing; Further be preferably more than the 0.1 μ m and below the 5 μ m, be preferably especially more than the 0.1 μ m and below the 4 μ m.Under above-mentioned bending condition; That is, use at allowing under the bending condition more than the radius-of-curvature of this resin substrate under 0～80 ℃ the TR under the situation of the resin substrate with hard coat of the present invention, the thickness of above-mentioned hard coat is during less than 0.1 μ m; Sometimes hard coat film is peeled off from resin substrate; In addition, when surpassing 6 μ m, hard coat can crack when bending machining or in the use under the case of bending sometimes.

For the resin substrate with hard coat of the present invention, in order further to improve rub resistance, film toughness, can on the hard coat of above-mentioned resin substrate with hard coat, apply staple is SiO ₂Finishing coat.As staple is SiO ₂The formation method of finishing coat, advantageous applications applies on above-mentioned hard coat gathers methods such as (perhydro-) silazane and solidified method, vapor deposition, sputter.

< resin substrate >

For resin as the material of the resin substrate that uses among the present invention, can enumerate out polycarbonate resin, polystyrene resin, aromatic polyester resins, acrylics, vibrin, polyarylate resin, halogenation dihydroxyphenyl propane and terepthaloyl moietie polycondensate, acrylated polyurethane resin, contain the acrylics of halogenation aryl etc.

In the middle of these, polycarbonate resin such as fragrant family polycarbonate resin or polymethylmethacrylate are that acrylics such as acrylics is preferred, and polycarbonate is preferred.And then in polycarbonate resin, dihydroxyphenyl propane is that polycarbonate resin is especially preferred.In addition, resin substrate can contain two or more above-mentioned such thermoplastic resins, the multilayer board that also can be to use these laminated resins to form more than 2 layers.In addition, not limiting the shape of resin substrate is special, can be dull and stereotyped, also can be crooked.In addition, the tone of resin substrate is preferably water white transparency or painted transparent.

In addition, the resin substrate with hard coat of the present invention be used under above-mentioned 0～80 ℃ TR this resin substrate allow the following time of bending condition more than the radius-of-curvature that the shape of resin substrate is dull and stereotyped.For the resin as the material of resin substrate, from allowing the aspect of radius-of-curvature, polycarbonate resin is preferred.In addition, the thickness of resin substrate is preferably 1～200mm, more preferably 1～50mm.

For the resin substrate with hard coat of the present invention, can between resin substrate and above-mentioned hard coat, have undercoat, in order to improve the adaptation of resin substrate and hard coat, preferably have undercoat.Do not limit undercoat is special, in the present invention, preferably be coated on the resin substrate and its drying is formed through the paint base composition that will contain acrylic acid polymer, UV light absorber and solvent.

As this acrylic acid polymer; Be selected from propenoate that the carbon number with alkyl is the alkyl below 6 and the methacrylic ester at least a for " principal monomer " (particularly; With respect to starting monomer totally is 90～100 moles of %, below identical) homopolymer or the multipolymer between these monomers be preferred.In addition, above-mentioned principal monomer and propenoate, at least a multipolymer in the methacrylic ester except that principal monomer also are preferred.As aforementioned monomer except that principal monomer, can enumerate out and have the alkyl of carbon number more than 7, propenoate, the methacrylic ester of the naphthenic base of carbon number below 12.In addition, can also use a spot of propenoate with the alkyl (for example hydroxyalkyl) that contains functional group, methacrylic ester copolymerization and the multipolymer that obtains with these monomers.As above-mentioned naphthenic base, can enumerate out cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, isobornyl, two cyclopentyl, two cyclopentenes oxygen base ethyls etc.

In the middle of these,, preferably, be that the principal monomer unit carries out the polymkeric substance that polymerization obtains to be selected from the alkyl methacrylate one or more as the acrylic acid polymer that uses among the present invention.In addition; Preferably; To be selected from alkyl carbon number in TEB 3K, n-BMA, methacrylic tert-butyl acrylate, Jia Jibingxisuanyizhi, the Propenoic acid, 2-methyl, isobutyl ester etc. is that one or more of alkyl methacrylate below 6 are that principal monomer carries out homopolymer or the multipolymer that polymerization obtains; More preferably; The homopolymer of TEB 3K, methacrylic tert-butyl acrylate, Jia Jibingxisuanyizhi etc. is with one or more the multipolymer that is selected from TEB 3K, n-BMA, Jia Jibingxisuanyizhi and the Propenoic acid, 2-methyl, isobutyl ester.

In addition, also can adopt more than one the polymerization/copolymerization in the acrylic monomer that is selected from Jie and has water-disintegrable silyl and/or SiOH group and the acrylic acid polymer that obtains by C-Si key bonding.

As aforementioned acrylic monomer, can enumerate out 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl dimethyl methyl TMOS, 3-methacryloxypropyl triethoxyl silane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl group methyl dimethoxysilane etc.

In addition, the preferred matter average molecular weight of these acrylic acid polymer that is used to form undercoat is more than 20000, more preferably more than 50000, preferably uses the acrylic acid polymer below 100 ten thousand.The matter average molecular weight can be given full play to adaptation, strength property as undercoat at the acrylic acid polymer of this scope, is preferred.

In undercoat,, can contain UV light absorber in order to suppress the resin substrate xanthochromia.As UV light absorber, can use the same material of UV light absorber that contains in the hard coating material composition with the invention described above.These can use a kind of, also can two or more combinations be used.The content of the UV light absorber in the undercoat is preferably 1～50 mass parts with respect to resinous principles such as acrylic acid polymer 100 mass parts, is preferably 1～30 mass parts especially.

Undercoat can further contain photostabilizer.As photostabilizer, can enumerate out hindered amines; Two (octyl phenyl) nickelous sulfide, 3, nickel complexes such as 5-di-tert-butyl-4-hydroxyl benzyl mono phosphoric acid ester ethanol nickel complex, nickel dibutyl dithiocarbamate.These can use two or more combinations.The content of the photostabilizer in the undercoat is preferably 0.1～50 mass parts with respect to resinous principles such as acrylic acid polymer 100 mass parts, is preferably 0.5～10 mass parts especially.

In being used to form the paint base composition of undercoat, contain solvent usually.As solvent, so long as can stably dissolve the solvent of aforementioned acrylic acid polymer, then not special the qualification.Particularly, can enumerate out ketones such as acetone, methylethylketone, MIBK, pimelinketone; THF, 1,4-diox, 1, ethers such as 2-glycol dimethyl ether; Ester classes such as vinyl acetic monomer, N-BUTYL ACETATE, acetic acid methoxyl group ethyl ester; Alcohols such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl cellosolve, 4-methyl-2-amylalcohol, butoxy ethanol, 1-methoxyl group-2-propyl alcohol, Pyranton; Hydro carbons such as normal hexane, normal heptane, octane-iso, benzene,toluene,xylene, gasoline, light oil, lam-oil; Acetonitrile, Nitromethane 99Min., water etc.These can use two or more combinations.

The amount of solvent is preferably 50～10000 mass parts with respect to resinous principles such as acrylic acid polymer 100 mass parts, is preferably 100～10000 mass parts especially.In addition, the content of the nonvolatile component in the paint base composition (solids component) is preferably 0.5～75 quality % with respect to total composition, is preferably 1～40 quality % especially.

Above-mentioned paint base composition can further contain additives such as flow agent, skimmer, viscous regulator.

As the method that paint base composition is coated on the resin substrate, not special the qualification can be enumerated out spraying method, dip coating, flow coat method etc.In addition, the exsiccant heating condition is not special to be limited to being used for, be preferably 50～140 ℃ following 5 minutes～3 hours.

For the undercoat that uses above-mentioned paint base composition on resin substrate, to form; When the thickness of undercoat is too small; Therefore sometimes the effect that improves the adaptation of resin substrate and hard coat can become insufficient, for for resin substrate and hard coat is fully bonding and keep that the thickness of necessity gets final product for the necessary amount of aforementioned additive.As the thickness of this undercoat, be preferably more than the 0.1 μ m and below the 10 μ m, be preferably especially more than the 2 μ m and below the 5 μ m.

Resin substrate with hard coat of the present invention when having undercoat, through on the undercoat that forms like this with the above-mentioned hard coat that likewise forms, can make the resin substrate with hard coat of the present invention.

The resin substrate with hard coat of the present invention that obtains like this has excellent weathering resistance and scuff resistance.About scuff resistance; Particularly; For the hard coating surface with resin substrate of hard coat of the present invention, the increasing amount of mist degree when making the abrasion of load 500g take turns the Taibo wear test of rotating 500 times according to JIS K5600 (5.9), that the test back is preceding with respect to test is to be preferred below 20%.

Embodiment

Below come further explain the present invention through embodiment, but the present invention does not receive any qualification of these embodiment.Wherein, example 1～34 is embodiment, and example 35～51 is a comparative example.In addition, in the present embodiment, the evaluation of organopolysiloxane is carried out according to project and method shown in following.

(1) is bonded to the number (B) of the hydroxyl of Siliciumatom/the be bonded to number (A) of the alkoxyl group of Siliciumatom

Below, because the organopolysiloxane that uses in an embodiment only has the methoxyl group (SiO-CH that is bonded to Siliciumatom ₃) as the organopolysiloxane that is bonded to the alkoxyl group of Siliciumatom, therefore,, use the Si-OH/SiO-CH that obtains through following method as above-mentioned (B)/(A) ₃Ratio.

The use infrared absorption spectrometer (FT-IR, Thermo Fisher Scientific K.K. makes, pattern: Avatar/Nicolet FT-IR360), by 2860cm ^-1Near derive from SiO-CH ₃Absorption and 900cm ^-1Near the area ratio of the absorption that derives from Si-OH is obtained Si-OH/SiO-CH ₃Ratio.

(2) analysis of the bonding state of the Siliciumatom in the organopolysiloxane

For the bonding state of the Siliciumatom in the organopolysiloxane, particularly, for the ratio of M unit, D unit, T unit, the unitary existence of Q and the existence ratio of T0～T3, the use magnetic nuclear resonance analyzer ( ²⁹Si-NMR: NEC's manufactured, ECP400) by ²⁹The peak area ratio of Si-NMR is obtained respectively.Condition determination is following: use polytetrafluoroethylene (PTFE) system 10mm φ sample hose, probe: T10, resonant frequency 79.42MHz, PW 10 μ sec, waiting time 20sec, cumulative frequency 1500 times, relaxation reagent: the Cr of 0.1 quality % (acac) ₃, external perimysium reference sample: TMS.In addition, derive from each structure ²⁹The chemical shift of Si-NMR at methyl be under the situation of organopolysiloxane as follows.

(M unit～Q unit)

M unit: 15～5ppm,

The D unit :-15～-25ppm,

The T unit :-35～-75ppm,

The Q unit :-90～-130ppm.

(T0～T3)

T0：-40～-41ppm，

T1：-49～-50ppm，

T2：-57～-59ppm，

T3：-66～-70ppm。

(3) number-average molecular weight Mn, matter average molecular weight Mw and dispersity Mw/Mn

(RI detects, post: Styragel guard column+HR1+HR4+HR5E, eluent: chloroform) obtain for GPC, the Waters2695 of Waters manufactured through gel permeation chromatography.

[1] organopolysiloxane (a) is synthetic

(example 1)

In the flask of 0.2L, adding methyl is that (trade(brand)name, chemical industrial company of SHIN-ETSU HANTOTAI makes silicone resin KR-220L, Si-OH/SiO-CH ₃=11.7, the unitary existence of each T is than being T0: T1: T2: T3=ND: ND: 28: 72, and Mn=1200; Mw=4720, Mw/Mn=3.93) (10g) and 1-butanols (10g) fully stir; Add acetic acid (10g), ion exchanged water (10g), further fully stir.This solution was stirred 1 hour down at 25 ℃, obtain organopolysiloxane (a) " MSi-1 ".Solution (the MSi-1 concentration: the preparation of [3] hard coating material composition of 25 quality %) stating after directly being used for that will contain this MSi-1.

For gained MSi-1, KR-220L next through FT-IR and as raw material compares, and results verification is to deriving from SiO-CH ₃The peak of group reduces and derives from the peak increase of Si-OH group.The Si-OH/SiO-CH of the MSi-1 that obtains by the peak area ratio of FT-IR ₃Than being 18.4.MSi-1 is made up of the T unit, by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: 0.9: 27.6: 71.5.In addition, the Mn of MSi-1 is 1200, Mw is 4720, Mw/Mn is 3.93.

(example 2)

Except temperature of reaction being changed to 40 ℃, through obtaining containing solution (the MSi-2 concentration: 25 quality %) of organopolysiloxane (a) " MSi-2 " with example 1 same method.The preparation of [3] hard coating material composition of stating after this solution directly is used for.

For gained MSi-2, KR-220L next through FT-IR and as raw material compares, and results verification is to deriving from SiO-CH ₃The peak of group reduces and derives from the peak increase of Si-OH group.The Si-OH/SiO-CH of the MSi-2 that obtains by the peak area ratio of FT-IR ₃Than being 58.7.MSi-2 is made up of the T unit, by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: trace: 25.1: 74.6.In addition, the Mn of MSi-2 is 1230, Mw is 4160, Mw/Mn is 3.83.

(example 3)

Except temperature of reaction being changed to 70 ℃, through obtaining containing solution (the MSi-3 concentration: 25 quality %) of organopolysiloxane (a) " MSi-3 " with example 1 same method.The preparation of [3] hard coating material composition of stating after this solution directly is used for.

For gained MSi-3, KR-220L next through FT-IR and as raw material compares, and results verification is to deriving from SiO-CH ₃The peak of group reduces and derives from the peak increase of Si-OH group.The Si-OH/SiO-CH of this MSi-3 that obtains by the peak area ratio of FT-IR ₃Than being 40.6.MSi-3 is made up of the T unit, by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: trace: 22.8: 77.0.In addition, the Mn of MSi-3 is 1140, Mw is 3750, Mw/Mn is 3.28.

(example 4)

Except changing to methyl as the KR-220L of raw material is that (chemical industrial company of SHIN-ETSU HANTOTAI makes silicone resin KR-500, and is unconfirmed to the peak that derives from the Si-OH group through FT-IR, is merely SiO-CH basically ₃The unitary existence of each T is than being T0: T1: T2: T3=ND: 15: 58: 27, and Mn=700, Mw=1240, Mw/Mn=1.77) in addition, through obtaining organopolysiloxane (a) " MSi-5 " with example 2 same methods.Solution (the MSi-5 concentration: the preparation of [3] hard coating material composition of 25 quality %) stating after directly being used for that will contain this MSi-5.

For gained MSi-5, KR-500 next through FT-IR and as raw material compares, and results verification is to deriving from SiO-CH ₃The peak of group reduces and derives from the peak appearance of Si-OH group.The Si-OH/SiO-CH of the MSi-5 that obtains by the peak area ratio of FT-IR ₃Than being 41.0.MSi-5 is made up of the T unit, by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: 1.1: 30.1: 68.8.The Mn of MSi-5 is 520, Mw is 1150, Mw/Mn is 2.22.

(example 5)

Except temperature of reaction being changed to 70 ℃, through obtaining containing solution (the MSi-6 concentration: 25 quality %) of organopolysiloxane (a) " MSi-6 " with example 4 same methods.The preparation of [3] hard coating material composition of stating after this solution directly is used for.

For gained MSi-6, KR-500 next through FT-IR and as raw material compares, and results verification is to deriving from SiO-CH ₃The peak of group reduces and derives from the peak appearance of Si-OH group.The Si-OH/SiO-CH of the MSi-6 that obtains by the peak area ratio of FT-IR ₃Than being 39.2.MSi-6 is made up of the T unit, by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: 0.8: 28.9: 70.3.The Mn of MSi-6 is 490, Mw is 1120, Mw/Mn is 2.28.

(example 35)

Except changing to methyl as the KR-220L of raw material is that (chemical industrial company of SHIN-ETSU HANTOTAI makes silicone resin KR-500, and is unconfirmed to the peak that derives from the Si-OH group through FT-IR, is merely SiO-CH basically ₃The unitary existence of each T is than being T0: T1: T2: T3=ND: 15: 58: 27, and Mn=700, Mw=1240, Mw/Mn=1.77) in addition, through obtaining organopolysiloxane " MSi-4 " with example 1 same method.Solution (the MSi-4 concentration: the preparation of [3] hard coating material composition of 25 quality %) stating after directly being used for that will contain this MSi-4.

For gained MSi-4, KR-500 next through FT-IR and as raw material compares, and results verification is to deriving from SiO-CH ₃The peak of group reduces and derives from the peak appearance of Si-OH group.The Si-OH/SiO-CH of the MSi-4 that obtains by the peak area ratio of FT-IR ₃Than being 15.3.It is master's bond structure that MSi-4 has with the T unit, by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: 15.1: 59.0: 25.8, T1: T2: T3 was outside the scope of organopolysiloxane of the present invention (a).The Mn of MSi-4 is 590, Mw is 1120, Mw/Mn is 1.90.

(example 36)

Methyl is that (chemical industrial company of SHIN-ETSU HANTOTAI makes silicone resin KR-220L, Si-OH/SiO-CH ₃=11.7, the unitary existence of each T is than being T0: T1: T2: T3=ND: ND: 28: 72, and Mn=1200, Mw=4720 Mw/Mn=3.93) is Si-OH/SiO-CH ₃At the extraneous organopolysiloxane of organopolysiloxane of the present invention (a),, be used for the preparation of following [3] hard coating material composition with this organopolysiloxane as example 36.

(example 37)

Methyl is that (chemical industrial company of SHIN-ETSU HANTOTAI makes silicone resin KR-500, and is unconfirmed to the peak that derives from the Si-OH group through FT-IR, is merely SiO-CH basically ₃The unitary existence of each T is than being T0: T1: T2: T3=ND: 15: 58: 27, and Mn=700, Mw=1240 Mw/Mn=1.77) is Si-OH/SiO-CH ₃And T1: T2: T3 all at the extraneous organopolysiloxane of organopolysiloxane of the present invention (a), with this organopolysiloxane as example 37, is used for the preparation of following [3] hard coating material composition.

The structural performance of each the routine organopolysiloxane that obtains like this is summarized in table 1.

[table 1]

[2] preparation of organopolysiloxane (b) synthetic and organopolysiloxane (b) composition solution (PSi-1)

In the flask of 1L, add water-dispersion colloidal silica (pH3.1, silicon dioxide microparticle solids component 35 quality %) and 0.2g acetic acid that 200g has the median size of about 15nm, add the 138g methyltrimethoxy silane.After stirring 1 hour, the pH of compsn is stabilized in 4.5.Positively make it in silicon-dioxide-methanol-water dispersion liquid, form the partly hydrolysed condenses over 4 days 25 ℃ of following slakings said composition.

The nonvolatile component of said composition is 40 quality %; Gained organopolysiloxane (below be called organopolysiloxane (b) " PSi-1 ") have with the T unit be the master bond structure (the unitary number of T: the total amount of M unit and D unit and Q unit number separately=100: 0), by ²⁹The unitary existence of each T that the chemical shift of Si-NMR is obtained is than being T0: T1: T2: T3=ND: 2: 54: 44.T0 body [the R-Si (OH) that in the gained organopolysiloxane, has the monomer shape hardly ₃] (R is an any monovalent organic radical group), confirm to be converted into the organopolysiloxane of oligopolymer shape basically fully to the methyltrimethoxy silane of raw material.The Mn of gained organopolysiloxane (b) PSi-1 is 400, Mw is 670, Mw/Mn is 1.68.Example is shown in the various structural performances of organopolysiloxane (b) PSi-1 on one hurdle, bottom of table 1 as a reference.

In the above-mentioned organopolysiloxane that obtains (b) PSi-1 solution (containing silicon dioxide microparticle (c)) 100 mass parts, add 4 mass parts benzophenone series UV light absorbers, 25 ℃ of following slakings more than 24 hours.Use 1-butanols, Virahol as diluting solvent, the preparation nonvolatile component is that 25 quality % (150 ℃, 45 minutes), viscosity are organopolysiloxane (b) the PSi-1 composition solution of 4.4mPas.

[3] preparation of hard coating material composition and evaluation

The preparation of (example 6～15) hard coating material composition HC-1～HC-6, HC-8～HC-11

The organopolysiloxane (a) of the routine 1-5 that in containing above-mentioned [1], obtains: in the solution of organopolysiloxane (a) MSi-1～MSi-3, MSi-5, MSi-6; With organopolysiloxane (b) the P Si-1 composition solution that obtains in the amount shown in the table 2 (quality %) compounding above-mentioned [2]; Thorough mixing, thus hard coating material composition HC-1～HC-6, HC-8～HC-11 (example 6～15) obtained.

[table 2]

(example 38～41)

25 quality %), methyl is silicone resin KR-500/1-butanol solution (concentration: in the solution 25 quality %) organopolysiloxane of the example 35～37 that in containing above-mentioned [1], obtains: the solution of organopolysiloxane MSi-4, methyl are silicone resin KR-220/1-butanol solution (concentration:; With organopolysiloxane (b) the PSi-1 composition solution that obtains in the amount shown in the table 3 (quality %) compounding above-mentioned [1]; Thorough mixing, thus hard coating material composition HC-7, HC-13, HC-14 (example 38,40,41) obtained.In addition, be HC-12 (example 39) with organopolysiloxane (b) the PSi-1 composition solution that obtains in above-mentioned [1].

[table 3]

(mensuration of the tensile stress of hard coating material composition (σ))

The curing overlay film that obtains carried out the mensuration of tensile stress (σ) in order to descend method for using the hard coating material composition that obtains in the hard coating material composition and routine 38～41 that obtains in above-mentioned routine 6～15.

Is that benchmark is contained in the prescribed position in the membrane stress determinator FLX-2320 (KLA Tencor manufactured) with the silicon chip of 4 inches of external diameters, thickness 525 ± 25 μ m with gulde edge (orientation flat), then at 25 ℃ of radius of curvature R b that measure this silicon chip down of envrionment temperature.

After the measurement, take out silicon chip, use spin-coating method on silicon chip, to be coated with the hard coating material composition HC-1 that obtains in above-mentioned routine 6, heating made it to be solidified to form curing overlay film in 1 hour under 120 ℃ then.Use and interfere thickness determinator Solid Lambda Thickness (Spectra Co-op manufactured), under the condition of specific refractory power 1.46, measure the thickness that is formed on the sclerosis overlay film on the silicon chip, the result is 2.2 μ m.

In addition; For on the surface of resin substrate, being coated with hard coating material composition HC-1 and filming of obtaining; Condition of cure is confirmed as follows: through FTIR determinator (Avatar/Nicolet FT-IR360; Thermo Fisher Scientific K.K. makes), use total reflection method to confirm wave number 910cm ^-1Near the disappearance of the absorption peak that produces by silanol group, thereby confirm.

For the silicon chip sample that has curing overlay film on the surface that obtains like this, identical with the situation of the independent radius-of-curvature (Rb) of above-mentioned measurement silicon chip, measure radius-of-curvature (Ra) down for 25 ℃ in envrionment temperature.

Use the above-mentioned Ra that records, Rb and following each illustrated factor to calculate the tensile stress (σ) shown in the following formula (1).

[mathematical expression 2]

σ = \frac{E \cdot h^{2}}{(1 - v) \cdot 6 \cdot R \cdot t} \cdot \cdot \cdot (1)

With likewise above-mentioned, make the hard coating material composition that obtains in the coating agent composition and routine 38～41 that obtains in the use-case 7～15 make the silicon chip sample that has curing overlay film on the surface respectively, measure its radius-of-curvature, calculate tensile stress (σ).The result is shown in table 4.

[table 4]

[4] has the making of the resin substrate of hard coat

[example 16]

Polycarbonate resin plate (CARBOGLASS (registered trademark) Polish Clear (trade(brand)name at thickness 3mm; Asahi Glass Co., Ltd makes)) on; Apply acrylic acid series priming paint SHP470 (Momentive Performance Materials Inc. makes, solids component 10 quality % solution) with impregnation method, make that dried thickness is 4～5 μ m; Use is set at the heat drying that 120 ℃ heated air circulation type moisture eliminator carried out 30 minutes, forms undercoat.Then,, after 25 ℃ of held 20 minutes, solidified 1 hour down, make the sample of resin substrate with hard coat at 120 ℃ with impregnation method coating hard coating material composition HC-1.The thickness of hard coat is 3 μ m.This sample is formed with acrylic acid series undercoat and hard coat on the two sides of polycarbonate plate.

[example 17～34]

Hard coating material composition HC-2～HC-6, HC-8～HC-11 with preparation in the impregnation method coating above-mentioned [3]; Make that the thickness of the hard coat after solidifying is the thickness shown in the table 5; In addition, use the sample of making resin substrate with example 1 same method with hard coat.

[example 42～49]

Except with the hard coating material composition HC-7 of preparation in the coating of the thickness shown in the table 6 above-mentioned [3], HC-12～HC-14 (example 38～41), use the sample of making resin substrate with example 16 same methods with hard coat.

[example 50,51]

In order to compare; As polycarbonate plate with commercially available silicon-type hard coat; Use is formed with the EC100XX (trade(brand)name of undercoat and silicon-type hard coat successively on the polycarbonate plate of thickness 5mm; TSUTSUNAKA PLASTIC INDUSTRY Co.; Ltd. make) (example 50) and LEXAN (registered trademark) the MARGUARD MR10 (trade(brand)name, SABIC Innovative Plastics manufactured) (example 51) that on the polycarbonate plate of thickness 3mm, is formed with undercoat and silicon-type hard coat successively.

[5] has the evaluation of the resin substrate sample of hard coat

The resin substrate sample with hard coat that obtains in each example for above-mentioned [4] carries out the evaluation of following project.Particularly, make the resin substrate sample that obtains in use-case 16～example 49, carry out the test of initial appearance, adaptation, scuff resistance and weather resistance (water tolerance, wet fastness, thermotolerance).About its evaluation result, example 16～34 is shown in table 5, and example 42～example 49 is shown in table 6.In addition, make the resin substrate sample that obtains in use-case 16～example 25 and routine 42～routine 46 carry out atmospheric exposure test.The result is shown in table 7.In addition, about the pressure pliability test that the resin substrate sample that obtains in use-case 26～example 34 and the example 47～example 51 is carried out, its evaluation result is shown in table 8.

< 1>outward appearance

With visual observation hard coat film (the overlay film integral body that undercoat and hard coat are lumped together is called " hard coat film "), judge have no abnormal.

Zero: no abnormal

*: hard coat film has crackle

< 2>thickness

Use the thickness of interfering thickness determinator (Spectra Co-op manufactured, Solid Lambda Thickness) to measure the hard coat in each sample.At this moment, specific refractory power is used the value of n=1.46.

< 3>scuff resistance

According to JIS K5600 (5.9); (the smart mechanism of Japan is done manufacturing at taber abrader; Pattern: ROTARY ABRASION TESTER) go up installation abrasion wheel CALIBRASE (registered trademark) CS-10F (TABER manufactured); Be determined at the mist degree (haze) that rotates under the 500g load after 500 times, to test back and the preceding mist degree difference Δ H of test ₅₀₀Be scuff resistance.Mist degree is according to JIS K7105 (6.4), and (Suga Test Instruments Co., Ltd. makes, pattern: HGM-2) measure with haze meter.

< 4>adaptation

According to JIS K5600 (5.6), use slasher, on hard coat film, depict vertical, horizontal each 11 otch with the interval of 1mm and make 100 checkers, (NICHIBAN CO., LTD. makes, and CT24) fully adheres to, and carries out stripping test then to make Cellotape.The grid number (X) that hard coat film is unstripped and residual is expressed as X/100.

< 5>water tolerance

For sample is flooded in 40 ℃ warm water crackle after 30 days, peel off have or not, gonorrhoea, estimate cosmetic variation and adaptation.

< 6>wet fastness

For the crackle of the hard coat film sample is placed 30 days in 50 ℃, the thermostatic bath of 95%RH after, peel off have or not, gonorrhoea, estimate cosmetic variation and adaptation.

< 7>thermotolerance

For the crackle that sample is heated the hard coat film after 30 days in 110 ℃ heated air circulation type baking oven, having or not of peeling off, estimate cosmetic variation and adaptation.

< 8>weathering resistance

Use light source to adopt accelerated weathering test machine (DAIPLA WINTES CO., the LTD. manufacturing of metal halide lamp; Daipla Metal Weather KU-R4); Example 16～example 25 and example 42～resin substrate sample that example obtains in 46 are applied irradiation, dewfall, dark these three kinds of conditions of light continuously, with visual valuation through having or not and peel off (weather-proof splitting resistance) after 792 hours with through the crackle of the hard coat film after 996 hours.For observed the crackle of hard coat film or the sample of peeling off in the past at 792 hours, write down its time.In addition, about the evaluation of weather-proof splitting resistance, before atmospheric exposure test, also implement.In addition, measure before the atmospheric exposure test/after yellowness factor and xanthochromia degree Δ YI, mist degree (haze) and mist degree difference Δ H.

Here, the condition of aforementioned irradiation is: at illumination 90mW/cm ², 63 ℃ of blackboard temperatures, relative humidity 70% condition under the 4 little time of irradiation; The condition of aforementioned dewfall is: irradiates light not makes blackboard temperature naturally cool to 30 ℃ and kept 4 hours from 70 ℃ under the condition of relative humidity 98%; The condition of aforementioned dark is: irradiates light not kept 4 hours under the condition of 70 ℃ of blackboard temperatures, relative humidity 90%.

< 8-1>weather-proof splitting resistance

With the outward appearance of the hard coat film after (initially)/atmospheric exposure test before the visual observation atmospheric exposure test, have no abnormal according to following benchmark judgement.

Zero: no abnormal

*: hard coat film has crackle

* *: hard coat film is peeled off

< 8-2>yellowness factor and xanthochromia degree Δ YI

By (initially) before the atmospheric exposure test, through after 792 hours, measure the result through the projection spectrographic after 996 hours and calculate yellowness factor; (Shimadzu Seisakusho Ltd.'s manufacturing SolidSpec-3700DUV) records said mensuration result with spectrophotometer according to the transmission measurement method of JISK7105 (6.3).With the yellowness factor before the atmospheric exposure test is YI ₀, with through after 792 hours with test before the difference of yellowness factor be Δ YI ₇₉₂, with through after 996 hours with test before the difference of yellowness factor be Δ YI ₉₉₆As determinating reference, and if Δ YI≤+ 5 would be judged to be qualified.

< 8-3>mist degree (haze) (unit: %) with mist degree difference Δ H

According to JIS K7105 (6.4), with haze meter (Suga Test Instruments Co., Ltd. makes, HGM-2) (initially) before the mensuration atmospheric exposure test, through after 792 hours, through the mist degree (haze) after 996 hours.After the evaluation test with the test before mist degree poor (Δ H).With the mist degree before the atmospheric exposure test is H ₀, with through after 792 hours with test before the difference of mist degree be Δ H ₇₉₂, with through after 996 hours with test before the difference of mist degree be Δ H ₉₉₆As determinating reference, and if Δ H≤+ 5% would be judged to be qualified.

< 9>force pliability test

Use the pressure pliability test anchor clamps that outside drawing has been shown among Fig. 1, the resin substrate sample that obtains in example 26～example 34 and example 47～routine 51 is forced pliability test in order to following method.

The radius of curvature R of allowing with respect to each thickness of slab in the cold-forming method of polycarbonate plate uses following formula (I) to represent at normal temperatures.

R＝180t…(I)

(in the formula, t is the thickness [mm] of polycarbonate substrate.)

Confirm to have the test film length and the regular length (among Fig. 1) of the resin substrate sample of hard coat according to this formula, make pressure pliability test anchor clamps 1 shown in Figure 1 to every kind of thickness of polycarbonate plate with " L " expression.For having used the polycarbonate plate sample thick polycarbonate plate of 3mm, that have hard coat, prepare the pressure bending jig of regular length L=185mm, the test film 2 that will cut into 20mm * 186mm is fixed on these anchor clamps.For having used the polycarbonate plate sample thick polycarbonate plate of 5mm, that have hard coat, prepare the pressure bending jig of regular length L=246mm, the test film 2 that will cut into 20mm * 247mm is fixed on these anchor clamps.

The polycarbonate plate sample of forcing on the bending jig 1 with hard coat is fixed in bending to be put in the constant temperature and humidity cabinet of 80 ℃ of temperature, relative humidity 95%; Remain on accelerated test under this state as forcing pliability test, bending crack patience is judged, forced to the crooked outward appearance of pressure after 240 hours below estimating.

The crooked outward appearance of < 9-1>pressure after 240 hours is judged

Observe hard coat film after 240 hours have flawless and polycarbonate substrate to have or not the set of fine crack (crazing crazing), according to following benchmark, has no abnormal with visual judgement.The resin substrate sample with hard coat that obtains in each example of above-mentioned [4] of using in the test in addition, is formed with the hard coat film 4 that is made up of undercoat and hard coat on the two sides as the polycarbonate substrate of resin substrate 3.For the generation of the crackle of hard coat film, if produce then be judged to be " * " at the hard coat film of one side at least.In addition, crazing (crazing) is that tensile stress owing to hard coat film produces.

Zero: no abnormal

*: hard coat film has crackle

* *: polycarbonate substrate has crazing (crazing)

< 9-2>forces bending crack patience

For no problem example in the judgement of the outward appearance after 240 hours, continue the crackle generation time that hard coat film is studied in test, the meliority with resin substrate of hard coat of the present invention is judged.

In addition, the resin substrate sample for obtaining in the example 26 of forcing to use in the pliability test～example 34 and routine 47～routine 51 carries out the test same with above-mentioned atmospheric exposure test with 996 hours durations of load application, estimates weather-proof splitting resistance.For observed the crackle of hard coat film or the sample of peeling off in the past at 996 hours, write down its time.

[table 5]

[table 6]

[table 7]

[table 8]

As shown in table 7, for the sample as the example 42～46 of comparative example, hard coat film has produced crackle when atmospheric exposure test 792 hours or 996 hours, and the outward appearance of hard coat film is judged to be " * ", is underproof.In addition; As shown in table 8; For sample as the example 47～example 49 of comparative example, atmospheric exposure test in the time of 996 hours hard coat film produced crackle or peeled off, for the sample of the example 50,51 of commercially available prod; Atmospheric exposure test in the time of 396 hours hard coat film produced crackle or overlay film, be underproof.On the other hand, be judged to be " zero ", can know that its weather-proof splitting resistance is superior to example 42～51 as the outward appearance of the hard coat film of atmospheric exposure test after 996 hours of the example 16～34 of embodiment.In addition, also no problem as the xanthochromia degree Δ YI and the mist degree difference Δ H of the example 16～25 of embodiment.

As shown in table 6; Example 42～49 as comparative example is no problem on initial appearance, adaptation, scuff resistance, and then example 42,43,45,47～49 has also kept water tolerance, wet fastness, thermotolerance in various endurance tests; But as stated; Was underproof in atmospheric exposure test in the time of 996 hours, therefore, had shown the meliority of hard coating material composition of the present invention.

Example 47～49 as comparative example is no problem on initial appearance, scuff resistance, but force pliability test after 240 hours outward appearance be judged to be " * " or " * * ", be underproof.On the other hand, as the pressure pliability test of the example 26,27,29～34 of embodiment after 240 hours outward appearance be judged to be " zero ", can know that its toughness of anti-the pressure also is superior to comparative example.Continue test, the result, the crackle generation time that produces on the hard coat film also significantly prolongs, and example 27 is 792 hours, and example 26,29～34 is more than 1000 hours, therefore, has shown the meliority with resin substrate of hard coat of the present invention.

About the hard coating material composition example 28 (all use HC-2) identical with routine 26,27; The thickness of hard coat is 8 μ m; Initial appearance, scuff resistance, atmospheric exposure test are no problem, force pliability test after 240 hours outward appearance be judged to be " * ", can know that it is not suitable for forcing crooked the use.

Can find out by above result; According to hard coating material composition of the present invention; Can obtain having the resin substrate of following hard coat, this hard coat has kept scuff resistance, water tolerance, wet fastness, with to compare thermotolerance, weather-proof splitting resistance more excellent in the past; It is no problem that optical property (xanthochromia degree Δ YI, mist degree difference Δ H) goes up, and weathering resistance improves.In addition, can know,, can obtain having resin substrate the hard coat of forcing crooked patience according to hard coating material composition of the present invention.Can consider that this is because through adding organopolysiloxane of the present invention (a), the stress in the time of can being suppressed at organopolysiloxane (b) thermofixation in the hard coating material composition produces.In addition, can think, can give thus in the hard coat film, make the resistibility of the be full of cracks of time spent and obtained resistance to bend(ing) through having for receiving thermal stresses, stress in bending with flexible.

Utilizability on the industry

Resin substrate with hard coat of the present invention can be used as the window glass for vehicle that is installed on automobile, the various vehicles, the building materials that are installed on buildingss such as house, building use with window glass.In addition, can be applied to force bending machining at normal temperatures and the building materials purposes used.

In addition, the japanese of submitting on March 27th, 2009 is gone out to be willing to that the full content of 2009-080355 number specification sheets, claims, accompanying drawing and summary quotes so far, incorporate into as the disclosure of specification sheets of the present invention.

Claims

1. organopolysiloxane; It presses the proportional meter of unit number; Ratio with T1: T2: T3=0～5: 15～40: 55～85 and T3/T2=1.5～4.0 contains the linkage containing silicon unit shown in following T1～T3; The intramolecular number (B) that is bonded to the hydroxyl of Siliciumatom is on average counted more than 12.0 by molecule with the ratio (B)/(A) that is bonded to the number (A) of the alkoxyl group of Siliciumatom, and the matter average molecular weight is 800～8000

T1：R-Si(-OX) ₂(-O ^*-)

T2：R-Si(-OX)(-O ^*-) ₂

T3：R-Si(-O ^*-) ₃

2. hard coating material composition; It contains and has the unitary organopolysiloxane of the linkage containing silicon shown in following T1～T3 (a) and have the unitary organopolysiloxane of the linkage containing silicon shown in following T1～T3 (b); Said organopolysiloxane (a) is the described organopolysiloxane of claim 1; Said organopolysiloxane (b) is the organopolysiloxane of 1/10～1/1.5 times matter average molecular weight with matter average molecular weight of said organopolysiloxane (a)

T1：R-Si(-OX) ₂(-O ^*-)

T2：R-Si(-OX)(-O ^*-) ₂

T3：R-Si(-O ^*-) ₃

3. hard coating material composition according to claim 2 wherein, with respect to total composition, contains the above solvent that is used to dissolve said organopolysiloxane (a) and said organopolysiloxane (b) of 20 quality %.

4. according to claim 2 or 3 described hard coating material compositions, wherein, said organopolysiloxane (b) is counted 1.5～30 times with the ratio of the content of said organopolysiloxane (a) by mass ratio.

5. according to claim 2 or 3 described hard coating material compositions, wherein, with respect to the total composition of having deducted solvent, the content of said organopolysiloxane (a) is 1～35 quality %, and the content of said organopolysiloxane (b) is 40～65 quality %.

6. according to each the described hard coating material composition in the claim 2～5, it further contains silicon dioxide microparticle (c).

7. according to each the described hard coating material composition in the claim 2～6, wherein, the matter average molecular weight of said organopolysiloxane (a) is 1000～6000.

8. according to claim 6 or 7 described hard coating material compositions; Wherein, With respect to the total composition of having deducted solvent; The content of said organopolysiloxane (a) is 1～35 quality %, and the content of said organopolysiloxane (b) is 40～65 quality %, and the content of said silicon dioxide microparticle (c) is 1～50 quality %.

9. according to each described hard coating material composition of claim 2～8, it can obtain the tensile stress σ shown in the following formula (1) is the curing overlay film below the 31Mpa,

[mathematical expression 1]

σ = \frac{E \cdot h^{2}}{(1 - v) \cdot 6 \cdot R \cdot t} \cdot \cdot \cdot (1)

In the formula (1); R is with the membrane stress determinator records under 25 ℃ of envrionment temperatures, silicon chip is independent radius-of-curvature poor [m] with the radius-of-curvature of the silicon chip sample that has curing overlay film on the surface that uses said silicon wafer to manufacture; Said curing overlay film is that the hard coating material composition as determinand is solidified to form under 120 ℃, 1 hour condition, and E/ (1/v) is by the elastic modulus E of silicon chip, the twin shaft Young's modulus that PR v calculates (crystal face (100): 1.805 * 10 ¹¹Pa), h is the thickness [m] of silicon chip, and t is the thickness [m] of curing overlay film.

10. the hard coat that resin substrate with hard coat, its at least one mask at resin substrate have the cured article by each the described hard coating material composition in the claim 2～9 to constitute.

11. the resin substrate with hard coat according to claim 10, wherein, the thickness of said hard coat is 0.1～20 μ m.

12. the resin substrate with hard coat according to claim 10, it is a tabular, can crookedly use at normal temperatures.

13. the resin substrate with hard coat according to claim 12, wherein, said crooked the use is under the condition of allowing more than the radius-of-curvature, to carry out.

14. according to claim 12 or 13 described resin substrates with hard coat, wherein, the thickness of said hard coat is 0.1～6 μ m.

15. each the described resin substrate with hard coat according in the claim 10～14 wherein, has undercoat between said resin substrate and the said hard coat.

16. according to each the described resin substrate with hard coat in the claim 10～15, wherein, the material of said resin substrate is a polycarbonate resin.